Substituted imidazolylmethyloxiranes and substituted imidazolypropenes their preparation and fungicides containing them

ABSTRACT

Substituted imidazolylmethyloxiranes and substituted imidazolylpropenes of the general formula I ##STR1## wherein R 1  and R 2  are alkyl, cycloalkyl, cycloalkenyl, tetrahydropyranyl, norbornyl, pyridyl, naphthyl, biphenyl or phenyl, 
     D is oxygen or a single bond, 
     E is H, F, Cl or Br, 
     X, Y and Z are hydrogen, halogen, nitro, cyano, alkyl, haloalkyl, alkoxy, unsubstituted or substituted amino, unsubstituted or substituted mercapto, acyl, alkoxycarbonyl, hydroxyalkyl or substituted or unsubstituted phenyl, and acid addition salts and metal complexes thereof tolerated by plants, 
     processes for their manufacture, and fungicides containing them.

This is a division of application Ser. No. 07,377,000, filed on July 7,1989, now U.S. Pat. No. 5,028618.

The present invention relates to novel substitutedimidazolylmethyloxiranes and substituted imidazolylpropenes, processesfor their preparation and fungicides containing them, and methods forcontrolling fungi.

It is known that imidazolyloxiranes, for examplecis-2-(imidazol-1-ylmethyl)-2-(4-fluorophenyl)-3-(2,6-difluorophenyl)-oxirane(DE-32 18 130) can be used as fungicides. However, the fungicidalactions are unsatisfactory.

We have found that substituted imidazolylmethyloxiranes and substitutedimidazolylpropenes of the formula I ##STR2## where R¹ and R² areidentical or different and are each C₁ 14 C₈ -alkyl, C₃ -C₈ -cycloalkyl,C₅ -C₈ -cycloalkenyl, tetrahydropyranyl, norbornyl, pyridyl, naphthyl,biphenyl or phenyl, and these radicals may be monosubstituted totrisubstituted by halogen, nitro, phenoxy, amino, alkyl, alkoxy orhaloalkyl, each of 1 to 4 carbon atoms, and D is O or a single bond, Eis H, F, Cl or Br and X, Y and Z are identical or different and are eachhydrogen, halogen, nitro, cyano, C₁ -C₃ -acyl, C₁ -C₃ -haloalkyl, C₁ -C₃-alkoxy, amino which is unsubstituted or substituted by C₁ -C₃ -alkyl orC₁ -C₃ -acyl, unsubstituted or C₁ -C₃ -alkyl-substituted mercapto, C₁-C₃ -acyl, C₁ -C₃ -alkoxycarbonyl, C₁ -C₃ -hydroxyalkyl or unsubstitutedor substituted phenyl, and X, Y and Z cannot simultaneously be hydrogen,and their plant-tolerated acid addition salts and metal complexes have abetter fungicidal action than known azole compounds.

The compounds of the formula I contain asymmetric carbon atoms and cantherefore occur as enantiomers and diastereomers. In the case of thenovel compounds, the mixtures of diastereomers can be separated in aconventional manner, for example on the basis of their differentsolubilities or by column chromatography, and can be isolated in pureform. The racemates of the novel compounds can be resolved by knownmethods, for example by salt formation with an optically active acid,separation of the diastereomeric salts and liberation of the enantiomersby means of a base. Both the pure diastereomers or enantiomers and themixtures of these obtained in the synthesis can be used as fungicides.

R¹ and R² are each, for example, C₁ -C₈ -alkyl, in particular C₁ -C₄-alkyl, such as methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl,tert-butyl, n-pentyl or neopentyl, 1-naphthyl, 2-naphthyl, p-biphenyl,phenyl, halophenyl, such as 2-chlorophenyl, 2-fluorophenyl,2-bromophenyl, 3-chlorophenyl, 3-bromophenyl, 3-fluorophenyl,4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl,2,4-dichlorophenyl,2,3-dichlorophenyl,2,5-dichlorophenyl,2,6-dichlorophenyl, 2-chloro-6-fluorophenyl or 2-chloro-4-fluorophenyl,C₁ -C₄ -alkoxyphenyl, such as 2-methoxyphenyl, 3-methoxyphenyl,4-methoxyphenyl, 2,4-dimethoxyphenyl or 3,4-dimethoxyphenyl, C₁ -C₄-alkylphenyl, such as 4-ethylphenyl, 4-isopropylphenyl,4-tert-butylphenyl or 4-tert-butoxyphenyl, 2-chloro-6-methylphenyl,3-phenoxyphenyl, 4-phenoxyphenyl, 3-nitrophenyl, 4-nitrophenyl,3-aminophenyl, 4-aminophenyl, 2-aminophenyl, 2-trifluoromethylphenyl,3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 3-pyridyl,tetrahydropyranyl, cyclopropyl, cyclopentyl, cyclohexyl, 2-cyclohexenyl,3-cyclohexenyl or norbornyl.

X, Y and Z are each, for example, hydrogen, methyl, ethyl, propyl,isopropyl, trifluoromethyl, methoxy, ethoxy, methylamino, dimethylamino,acetylamino, diacetylamino, methylthio, acetyl, methoxyacetyl, phenyl,halophenyl, chlorophenyl or hydroxyethyl, and X, Y and Z cannotsimultaneously be hydrogen, ie. one or more of the radicals X, Y and Zdiffer from hydrogen.

Acid addition salts are, for example, the hydrochlorides, bromides,sulfates, nitrates, phosphates, oxalates and dodecylbenzenesulfonates.The activity of the salts is attributable to the cation, so that theanion is generally unimportant. The novel active ingredients salts areprepared by reacting an imidazolylmethyloxirane (I) with an acid.

Metal complexes of the active ingredients I or their salts can beformed, for example, with copper, zinc, tin, manganese, iron, cobalt ornickel, by reacting the imidazolylmethyloxirane with a correspondingmetal salt, for example with copper sulfate, zinc chloride, tin chlorideor manganese sulfate.

The compounds of the formula I in which D is O and E is H can beprepared, for example by

a) reacting a compound of the formula II ##STR3## where R¹ and R² havethe abovementioned meanings and L is a leaving group which can besubstituted by a nucleophile (eg. halogen or OH), with a compound of theformula III ##STR4## where Me is hydrogen, a metal atom (eg. Na or K) ortrimethylsilyl and X, Y and Z have the abovementioned meanings, or

b) converting a compound of the formula IV ##STR5## where R¹, R², X, Yand Z have the abovementioned meanings, into the epoxide.

If Me is hydrogen, reaction a) is carried out, for example, in thepresence or absence of a base and in the presence or absence of asolvent or diluent, with or without the addition of a reactionaccelerator, at from 10° to 120° C. The preferred solvents and diluentsinclude ketones, such as acetone, methyl ethyl ketone and cyclohexanone,nitriles, such as acetonitrile and propionitrile, alcohols, such asmethanol, ethanol, isopropanol, n-butanol and glycol, esters, such asethyl acetate, methyl acetate and butyl acetate, ethers, such astetrahydrofuran, diethyl ether, dimethoxyethane, dioxane and diisopropylether, amides, such as dimethylformamide, dimethylacetamide andN-methylpyrrolidone, and dimethyl sulfoxide, sulfolane and mixtures ofthese.

Suitable bases, which may also be used as acid acceptors in the reactionare, for example, alkali metal hydroxides, such as lithium hydroxide,sodium hydroxide or potassium hydroxide, alkali metal carbonates, suchas sodium carbonate, potassium carbonate or cesium carbonate, or sodiumbicarbonate, potassium bicarbonate, cesium bicarbonate, pyridine or4-dimethylaminopyridine. However, other conventional bases may also beused.

Preferred reaction accelerators are metal halides, such as sodium iodideor potassium iodide, quaternary ammonium salts, such astetrabutylammonium chloride, bromide, iodide or bisulfate,benzyltriethylammonium chloride or bromide, and crown ethers, such as12-crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown-6 ordicyclohexano-18-crown-6.

The reaction is generally carried out at, for example, from 20° to 150°C., under atmospheric or super atmospheric pressure, continuously orbatchwise.

If Me is a metal atom, reaction a) is carried out, for example, in thepresence or absence of a solvent or diluent and with or without theaddition of a strong inorganic or organic base, at from -10° to 120° C.The preferred solvents and diluents include amides, such asdimethylformamide, diethylformamide, dimethylacetamide,diethylacetamide, N-methylpyrrolidone, hexamethylphosphorotriamide,sulfoxides, such as dimethyl sulfoxide, and finally sulfolane.

Suitable bases, which may also be used as acid acceptors in thereaction, are, for example, alkali metal hydrides, such as lithiumhydride, sodium hydride and potassium hydride, alkali metal amides, suchas sodium amide and potassium amide, as well as sodium tert-butoxide,potassium tert-butoxide, triphenylmethyllithium, triphenylmethylsodium,triphenylmethylpotassium, naphthalenelithium, naphthalenesodium andnaphthalenepotassium.

Examples of suitable diluents for reaction b) are polar organicsolvents, such as nitriles, eg. acetonitrile, sulfoxides, eg. dimethylsulfoxide, formamides, eg. dimethylformamide, ketones, eg. acetone,ethers, eg. diethyl ether or tetrahydrofuram, and in particularchlorohydrocarbons, eg. methylene chloride and chloroform.

The reaction is carried out in general at, for example, from 0° to 100°C., preferably from 20° to 80° C. In the presence of a solvent, it isadvantageously carried out at the boiling point of the particularsolvent.

The novel starting compounds II are obtained, for example, byepoxidation of the corresponding olefins V ##STR6## (cf. G. Dittus inHouben-Weyl-Muller, Methoden der Organischen Chemie, Georg ThiemeVerlag, Stuttgart, 1965, Vol. VI, 3, page 385 et seq.).

The compound V is prepared by halogenating or oxidizing olefins of theformula IX ##STR7## by know methods in the allyl position.

Suitable halogenating reagents are N-chloro- and N-bromosuccinimide inhalohydrocarbons, such as carbon tetrachloride, trichloroethane ormethylene chloride, temperatures of from 20° to 100° C. being employed.For the allyl oxidation, peresters, such as tert-butyl perbenzoate ortert-butyl peracetate, are used in the presence of a heavy metal salt,eg. copper(I) chloride or copper(I) bromide. The reaction is carried outin an inert solvent at from 10° to 100° C.

The allyl halides or alcohols V thus obtained are then converted intothe corresponding epoxides II (L=halogen or OH). For this purpose, theolefins V are oxidized with a peroxycarboxylic acid, such as perbenzoicacid, 3-chloroperbenzoic acid, 4-nitroperbenzoic acid, monoperphthalicacid, peracetic acid, perpropionic acid, permaleic acid, monopersuccinicacid, perpelargonic acid or trifluoroperacetic acid, in an inertsolvent, preferably a chlorohydrocarbon, eg. methylene chloride,chloroform, carbon tetrachloride or dichloroethane, or, if required, inacetic acid, ethyl acetate, acetone or dimethylformamide, in thepresence or absence of a buffer, such as sodium acetate, sodiumcarbonate, disodium hydrogen phosphate or Triton B. The reaction iscarried out at from 10° to 100° C. and, if required, is catalyzed with,for example, iodine, sodium tungstate or light. Alkaline solutions ofhydrogen peroxide (about 30% strength) in methanol, ethanol, acetone oracetonitrile, at from 25° to 30° C., and alkyl hydroperoxides, eg.tert-butyl hydroperoxide, with the addition of a catalyst, eg. sodiumtungstate, pertungstic acid, molybdenum hexacarbonyl or vanadylacetylacetonate, are also suitable for the oxidation. Some of the stateoxidizing agents can be produced in situ.

While the resulting epoxyhalides II (L=halogen) can be reactedimmediately by process a), the corresponding epoxyalcohols II (L=OH) areconverted into, for example, reactive esters, which are then reactedwith the compounds III by process a).

The reactive esters which can be reacted with III are prepared bygenerally known methods (Houben-Weyl-Muller, Methoden der organischenChemie, Georg Thieme Verlag, Stuttgart, 1955, Volume 9, pages 388, 663and 671). Examples of such esters are methanesulfonates,trifluoromethanesulfonates, 2,2,2-trifluoroethanesulfonates,nonafluorobutanesulfonates, 4-methylbenzenesulfonates,4-bromobenzenesulfonates, 4-nitrobenzenesulfonates andbenzenesulfonates.

The compounds V can be prepared by generally known processes of olefinsynthesis (Houben-Weyl-Muller, Methoden der organischen Chemie, GeorgThieme Verlag, Stuttgart, 1972, Vol. V, 1b).

The compounds of the formula IV ##STR8## are obtained, for example, bya) reacting a compound of the formula V ##STR9## where R¹ and R² havethe abovementioned meanings and L is a leaving group which can besubstituted by a nucleophile, with a compound of the formula III##STR10## where Me is hydrogen, a metal atom or trimethylsilyl and X, Yand Z have the above mentioned meanings, or reacting a compound of theformula VI ##STR11## where R¹, X, Y and Z have the abovementionedmeanings, with a compound of the formula VII ##STR12## where R² has thesame meanings as in formula I and R³, R⁴ and R⁵ may be identical ordifferent and are each phenyl, p-carboxyphenyl, p-dimethylaminophenyl,dimethylamino, piperidino, morpholino, alkyl of 1 to

3 carbon atoms or cyclohexyl.

The compounds of the formula I in which E is F, Cl or Br can beprepared, for example, by reacting a compound of the formula VIII##STR13## where R¹, R² and D have the state meanings, with a compound ofthe formula III ##STR14## where X, Y, Z and Me have the abovementionedmeanings, in the presence of a thionyl halide.

The reaction is carried out, for example, in the presence or absence ofa solvent or diluent at from -30° to 80° C. The preferred solvents anddiluents include nitriles, such as acetonitrile or, propionitrile,ethers, such as tetrahydrofuran, diethyl ether, dimethoxyethane, dioxaneor diisopropyl ether, and in particular hydrocarbons andchlorohydrocarbons, such as pentane, hexane, toluene, methylenechloride, chloroform, carbon tetrachloride or dichloroethane, ormixtures of these.

The novel starting compounds VIII in which D is O are obtained, forexample, by epoxidation of the corresponding olefins X ##STR15## (cf. G.Dittus in Houben-Weyl-Muller, Methoden der Organischen Chemie, GeorgThieme Verlag, Stuttgart, 1965, Vol. VI, 3, page 38 et seq.).

The compounds X can be prepared by generally known methods of aldehydesynthesis (Houben-Weyl-Muller, Methoden der Organischen Chemie, GeorgThieme Verlag, Stuttgart, 1983, Vol. E3).

The Examples which follow illustrate the preparation of the activeingredients.

I. PREPARATION OF THE STARTING MATERIALS EXAMPLE A

8.4 g of sodium hydroxide in 40 ml of water are added to a solution of85.5 g of 2-trifluoromethylbenzaldehyde in 300 ml of methanol. Thereaction mixture is cooled to 10° C. and 69 g of4-fluorophenylacetaldehyde are rapidly added dropwise, the temperatureof the solution not exceeding 30° C. After stirring has been carried outfor two hours at room temperature, 300 ml of water are added to thecolorless reaction solution, and the resulting emulsion is extracted byshaking with methyl tert-butyl ether. The organic phase is separatedoff, dried over sodium sulfate and evaporated down under reducedpressure. In the subsequent distillation of the remaining residue, 96 g(65%) of E-2-(4-fluorophenyl)-3-(2-trifluoromethylphenyl)-propenal areobtained at 116° C./0.3 mbar.

EXAMPLE B

96 g of E-2-(-4-fluorophenyl)-3-(2-trifluoromethylphenyl)-propenal aredissolved in 300 ml of methanol and 2.3 ml of concentrated sodiumhydroxide solution are added. The reaction solution is stirred at 0° C.while 27.7 g of about 50% strength hydrogen peroxide are slowly addeddropwise, the internal temperature not exceeding 30° C. After the end ofthe addition, stirring is continued for 6 hours at room temperature (20°C.), after which 5 g of sodium borohydride, which has been dissolved ina little 10% strength sodium hydroxide solution, are added. After thereaction mixture has been stirred for 18 hours at room temperature, 100ml of water are added to the solution and the resulting emulsion isextracted by shaking with methylene chloride. The organic phase isolatedis then dried over sodium sulfate and evaporated down. 90 g (89%) ofcis-2-hydroxymethyl-2-(4-fluorophenyl)-3-(2-trifluoromethylphenyl)-oxiraneare obtained.

EXAMPLE C

61 g of 4-methlbenzenesulfonyl chloride are added to a solution of 90 gofcis-2-hydroxymethyl-2-(4-fluorophenyl)-3-(2-trifluoromethylphenyl)-oxiranein 300 ml of methylene chloride and 58 g of triethylamine at roomtemperature. After 24 hours, the reaction mixture is washed with aqueoussodium bicarbonate solution and water and evaporated down under reducedpressure. The residue gives 128.4 g (95%) ofcis-2-(4-methylphenylsulfonyloxymethyl)-2-(4-fluorophenyl)-3-(2-trifluoromethylphenyl)-oxirane,which is then further processed with triazole.

EXAMPLE D

7.3 g of sodium borohydride, which has been dissolved in a little 10%strength sodium hydroxide solution are added to a solution of 150 g ofE-2-(4-fluorophenyl)-3-(2-chlorophenyl)-propenal (prepared as describedin Example A) in 600 ml of isopropanol at 0° C. After the reactionmixture has been stirred for two hours at room temperature, 300 ml ofwater are added to the solution and the resulting emulsion is extractedby shaking with methylene chloride. The organic phase isolated is thendried over sodium sulfate and evaporated down. 150.7 g (100%) ofE-2-(4-fluorophenyl)-3-(2-chlorophenyl)-prop-2-enol are obtained.

EXAMPLE E

103.1 g of E-2-(4-fluoropehnyl)-3-(2-chlorophenyl)-prop-2-enol aredissolved in 700 ml of methyl tert-butyl ether, and 2 ml of pyridine areadded. The reaction solution is stirred under a nitrogen atmosphere at0° C., while 27.2 g of phosphorus tribromide are added in the course of90 minutes. After the end of the addition, the mixture is refluxed fortwo hours and then poured onto 500 ml of water and extracted severaltimes with methyl tert-butyl ether. The organic phase is washed withsodium bicarbonate solution and water and dried over sodium sulfate, andthe solvent is evaporated down under reduced pressure. 77.2 g (61%) ofE-1-bromo-2-(4-fluorophenyl)-3-(2-chlorophenyl)-prop-2-ene of meltingpoint 68° C. are obtained from ethanol.

EXAMPLE F

77.2 g of E-1-bromo-2-(4-fluorophenyl)-3-(2-chlorophenyl)-prop-2-ene areheated at 180° C. for one hour. The reaction mixture is cooled to roomtemperature and 200 ml of ethanol are added. Thereafter, 10 g of activecarbon are added and the mixture is heated to 50° C. and filtered whilehot. 26.9 g (35%) ofZ-1-bromo-2-(4-fluorophenyl)-3-(2-chlorophenyl)-prop-2-ene of meltingpoint 73°-75° C. are obtained from ethanol.

EXAMPLE G

78.2 g of E-2-(4-fluorophenyl)-3-(2-chlorophenyl)-propenal are dissolvedin 300 ml of methanol, and 1 ml of concentrated sodium hydroxidesolution is added. The reaction solution is stirred at 0° C. while 20.5g of about 50% strength hydrogen peroxide are slowing added dropwise,the internal temperature not exceeding 30° C. After the end of theaddition, the mixture is stirred for six hours at room temperature,after which 100 ml of water are added and the resulting emulsion isextracted by shaking with methyl tert-butyl ether. The organic phaseisolated is then dried over sodium sulfate and evaporated down. 52.5 g(63%) of cis-2-formyl-2-(4-fluorophenyl)-3-(2-chlorophenyl)-oxirane areobtained.

II. PREPARATION OF THE END PRODUCTS EXAMPLE 1

55 g of 4,5-dichloroimidazole and 9.5 g of sodium hydride (80% strengthdispersion in mineral oil) are suspended in 300 ml ofN,N-dimethylformamide and a solution of 128.4 g ofcis-2-(4-methylphenylsulfonyloxymethyl)-2-(4-fluorophenyl)-3-(2-trifluoromethylphenyl)-oxirane in 200 ml of N,N-dimethylformamide is added at roomtemperature. After eight hours, the reaction solution is poured ontowater and extracted with methyl tert-butyl ether. The organic phase iswashed with water and dried over sodium sulfate and the solvent isevaporated down under reduce pressure. 86.4 g (76%) ofcis-2-(4,5-dichloroimidazol-1-ylmethyl)-2-(4-fluorophenyl)-3-(2-trifluoromethylphenyl)-oxiraneof melting point 158° C. (compound) No. 1) are obtained from methyltert-butyl ether/n-hexane.

The compounds listed in Table 1 can be prepared similarly to Example 1.

EXAMPLE 2

15 g of 5-nitroimidazole and 31 g of potassium carbonate are added to asolution of 7.5 g ofZ-1-bromo-2-(4-fluorophenyl)-3-(2-chlorophenyl)-prop-2-ene in 40 ml ofdimethylformamide. After the reaction mixture has been stirred for 24hours at room temperature, 50 ml of water are added and the mixture isextracted several times with methyl tert-butyl ether; the organic phaseis washed with water, dried over sodium sulfate and evaporated downunder reduced pressure. 6.7 g (81%) ofZ-1-(5-nitroimidazol-1-yl)-2-(4-fluorophenyl)-3-(2-chlorophenyl)-prop-2-eneof melting point 161°-165° C. (compound No. 1a) are obtained from methyltert-butyl ether/n-hexane.

The compounds listed in Table 2 can be prepared similarly to Example 2.

EXAMPLE 3

13.1 g of thionyl chloride are added to a solution of 27.7 g of methyl4-imidazolecarboxylate in 150 ml of methylene chloride at 0° C. Afterthe end of the addition, the mixture is stirred for 30 minutes at roomtemperature and 18.5 g ofcis-2-formyl-2-(4-fluorophenyl)-3-(2-chlorophenyl)-oxirane are thenadded. After the reaction mixture has been stirred for 12-15 hours atroom temperature, 100 ml of water are added to the solution and theorganic phase is separated off. The remaining aqueous phase is extractedtwice by shaking with methylene chloride and the collected organicphases are washed twice with saturated sodium bicarbonate solution. Theorganic phase isolated is then dried over sodium sulfate and evaporateddown. 14.3 g (53%) ofcis-2-[1-(4-methoxycarbonylimidazol-1-yl)-1-chloromethyl]-2-(4-fluorophenyl)-3-(2-chlorophenyl)-oxiraneof melting point 199°-203° C. (compound No. 25) are obtained from methyltert-butyl ether.

The compounds listed is Table 1 can be prepared similarly to Example 3.

EXAMPLE 4

13.1 g of thionyl chloride are added to a solution of 30.1 g of4,5-dichloroimidazole in 150 ml of methylene chloride at 0° C. After theend of the addition, the mixture is stirred for 30 minutes at roomtemperature and 17.4 g ofE-2-(4-fluorophenyl)-3-(2-chlorophenyl)-propenal are then added. Afterthe reaction mixture has been stirred for 12-15 hours at roomtemperature, 100 ml of water are added to the solution and the organicphase is separated off. The remaining aqueous phase is extracted twiceby shaking with methylene chloride and the collected organic phases arewashed twice with saturated sodium bicarbonate solution. The organicphase isolated is then dried over sodium sulfate and evaporated down,and the residue is purified by chromatography over silica gel using 9:1ethyl acetate n-hexane. 24.8 (89%) ofE-1-chloro-1-(4,5-dichloroimidazol-1-yl)-2-(4-fluorophenyl)-3-(2-chlorophenyl)-prop-2-ene(compound No. 8a) are obtained.

The compounds listed in Table 2 can be prepared similarly to Example 4.

                                      TABLE 1                                     __________________________________________________________________________     ##STR16##                                                                    Ex. R.sup.1 R.sup.2  E X    Y    Z   m.p./IR    Isomer                        __________________________________________________________________________    1   4-FC.sub.6 H.sub.4                                                                    2-CF.sub.3C.sub.6 H.sub.4                                                              H Cl   Cl   H   158° C.                                                                           cis                           2   4-FC.sub.6 H.sub.4                                                                    2-CF.sub.3C.sub.6 H.sub.4                                                              H H    CO.sub.2 CH.sub.3                                                                  H   1699, 1514, 1315                                                                         cis                                                                1222, 1123, 771, cm.sup.-1               3   4-FC.sub.6 H.sub.4                                                                    2-CF.sub.3C.sub.6 H.sub.4                                                              H Cl   CH.sub.3                                                                           H   164-167° C.                                                                       cis                           4   4-FC.sub.6 H.sub.4                                                                    2-CF.sub.3C.sub.6 H.sub.4                                                              H H    H    CH.sub.3                                     5   4-FC.sub.6 H.sub.4                                                                    2-CF.sub.3C.sub.6 H.sub.4                                                              H H    CN   H                                            6   4-FC.sub.6 H.sub.4                                                                    2-CF.sub.3C.sub.6 H.sub.4                                                              H NO.sub.2                                                                           H    H                                            7   4-FC.sub.6 H.sub.4                                                                    2-CF.sub.3C.sub.6 H.sub.4                                                              H H    CH.sub.3                                                                           H                                            8   4-FC.sub.6 H.sub.4                                                                    2-CF.sub.3C.sub.6 H.sub.4                                                              Cl                                                                              Cl   Cl   H                                            9   4-FC.sub.6 H.sub.4                                                                    2-CF.sub.3C.sub.6 H.sub.4                                                              Cl                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            10  4-FC.sub.6 H.sub.4                                                                    2-CF.sub.3C.sub.6 H.sub.4                                                              Cl                                                                              Cl   CH.sub.3                                                                           H                                            11  4-FC.sub.6 H.sub.4                                                                    2-CF.sub.3C.sub.6 H.sub.4                                                              Cl                                                                              H    H    CH.sub.3                                     12  4-FC.sub.6 H.sub.4                                                                    2-CF.sub.3C.sub.6 H.sub.4                                                              Cl                                                                              H    CN   H                                            13  4-FC.sub.6 H.sub.4                                                                    2-CF.sub.3C.sub.6 H.sub.4                                                              Cl                                                                              NO.sub.2                                                                           H    H                                            14  4-FC.sub.6 H.sub.4                                                                    2-CF.sub.3C.sub.6 H.sub.4                                                              Br                                                                              Cl   Cl   H                                            15  4-FC.sub.6 H.sub.4                                                                    2-CF.sub.3C.sub.6 H.sub.4                                                              Br                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            16  4-FC.sub.6 H.sub.4                                                                    2-CF.sub.3C.sub.6 H.sub.4                                                              Br                                                                              H    CH.sub.3                                                                           H                                            17  4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    H Cl   Cl   H   108-115° C.                                                                       cis                           18  4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    H H    CO.sub.2 CH.sub.3                                                                  H   resin      cis                           19  4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    H Cl   CH.sub.3                                                                           H   112-113° C.                                                                       cis                           20  4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    H H    H    CH.sub.3                                                                          100-103° C.                                                                       cis                           21  4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    H H    CN   H   128-131° C.                                                                       cis                           22  4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    H H    NO.sub.2                                                                           H   206-208° C.                                                                       cis                           23  4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    H H    CH.sub.3                                                                           H   resin      cis                           24  4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    Cl                                                                              Cl   Cl   H   156-158° C.                                                                       cis                           25  4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    Cl                                                                              H    CO.sub.2 CH.sub.3                                                                  H   199-203° C.                                                                       cis                           26  4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    Cl                                                                              Cl   CH.sub.3                                                                           H   146-156° C.                                                                       D1:D2 = 1:1                   27  4-FC.sub.6 H.sub. 4                                                                   2-ClC.sub.6 H.sub.4                                                                    Cl                                                                              H    H    CH.sub.3                                     28  4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    Cl                                                                              H    CN   H   50-60° C.                                                                         D1:D2 = 2:1                   29  4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    Cl                                                                              NO.sub.2                                                                           H    H                                            30  4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    Cl                                                                              H    CH.sub.3                                                                           H                                            31  4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    Br                                                                              Cl   Cl   H   115-122° C.                                                                       D1:D2 = 4:1                   32  4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    Br                                                                              H    CO.sub.2 CH.sub.3                                                                  H   162° C.                                                                           cis                           33  4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    Br                                                                              Cl   CH.sub.3                                                                           H                                            34  4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    Br                                                                              H    H    CH.sub.3                                     35  4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    Br                                                                              H    CN   H                                            36  4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    Br                                                                              NO.sub.2                                                                           H    H                                            37  4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    H Cl   Cl   H   146-148° C.                                                                       cis                           38  4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    H H    CO.sub.2 CH.sub.3                                                                  H   138-141° C.                                                                       cis                           39  4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    H Cl   CH.sub.3                                                                           H   124-126° C.                                                                       cis                           40  4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    H H    H    CH.sub.3                                     41  4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    H H    CN   H                                            42  4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    H NO.sub.2                                                                           H    H                                            43  4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    H H    COCH.sub.3                                                                         H   127-130° C.                                                                       cis                           44  4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    Cl                                                                              Cl   Cl   H                                            45  4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    Cl                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            46  4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    Cl                                                                              Cl   CH.sub.3                                                                           H                                            47  4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    Cl                                                                              H    H    CH.sub.3                                     48  4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    Cl                                                                              H    CN   H                                            49  4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    Cl                                                                              NO.sub.2                                                                           H    H                                            50  4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    Br                                                                              Cl   Cl   H                                            51  4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    Br                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            52  4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    Br                                                                              Cl   CH.sub.3                                                                           H                                            53  4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    Br                                                                              H    H    CH.sub.3                                     54  4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    Br                                                                              H    CN   H                                            55  4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    Br                                                                              NO.sub.2                                                                           H    H                                            56  4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    Br                                                                              H    CH.sub.3                                                                           H                                            57  4-FC.sub.6 H.sub.4                                                                    2-Cl-4-FC.sub.6 H.sub.3                                                                H Cl   Cl   H   105-110° C.                                                                       cis                           58  4-FC.sub.6 H.sub.4                                                                    2-Cl-4-FC.sub.6 H.sub.3                                                                H H    CO.sub.2 CH.sub.3                                                                  H   resin      cis                           59  4-FC.sub.6 H.sub.4                                                                    2-Cl-4-FC.sub.6 H.sub.3                                                                H Cl   CH.sub.3                                                                           H   150° C.                                                                           cis                           60  4-FC.sub.6 H.sub.4                                                                    2-Cl-4-FC.sub.6 H.sub.3                                                                H H    H    CH.sub.3                                     61  4-FC.sub.6 H.sub.4                                                                    2-Cl-4-FC.sub.6 H.sub. 3                                                               H H    CN   H                                            62  4-FC.sub.6 H.sub.4                                                                    2-Cl-4-FC.sub.6 H.sub.3                                                                H NO.sub.2                                                                           H    H                                            63  4-FC.sub.6 H.sub.4                                                                    2-Cl-4-FC.sub.6 H.sub.3                                                                H H    CH.sub.3                                                                           H                                            64  4-FC.sub.6 H.sub.4                                                                    2-Cl-4-FC.sub.6 H.sub.3                                                                Cl                                                                              Cl   Cl   H   145-149° C.                                                                       D1:D2 = 2:1                   65  4-FC.sub.6 H.sub.4                                                                    2-Cl-4-FC.sub.6 H.sub.3                                                                Cl                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            66  4-FC.sub.6 H.sub.4                                                                    2-Cl-4-FC.sub.6 H.sub.3                                                                Cl                                                                              Cl   CH.sub.3                                                                           H                                            67  4-FC.sub.6 H.sub.4                                                                    2-Cl-4-FC.sub.6 H.sub.3                                                                Cl                                                                              H    H    CH.sub.3                                     68  4-FC.sub.6 H.sub.4                                                                    2-Cl-4-FC.sub.6 H.sub.3                                                                Cl                                                                              H    CN   H                                            69  4-FC.sub.6 H.sub.4                                                                    2-Cl-4-FC.sub.6 H.sub.3                                                                Cl                                                                              NO.sub.2                                                                           H    H                                            70  4-FC.sub.6 H.sub.4                                                                    2-Cl-4-FC.sub.6 H.sub.3                                                                Cl                                                                              H    CH.sub.3                                                                           H                                            71  4-FC.sub.6 H.sub.4                                                                    2-Cl-4-FC.sub.6 H.sub.3                                                                Br                                                                              Cl   Cl   H                                            72  4-FC.sub.6 H.sub.4                                                                    2-Cl-4-FC.sub.6 H.sub.3                                                                Br                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            73  4-FC.sub.6 H.sub.4                                                                    2-Cl-4-FC.sub.6 H.sub. 3                                                               Br                                                                              Cl   CH.sub.3                                                                           H                                            74  4-FC.sub.6 H.sub.4                                                                    2-Cl-4-FC.sub.6 H.sub.3                                                                Br                                                                              H    H    CH.sub.3                                     75  4-FC.sub.6 H.sub.4                                                                    2-Cl-4-FC.sub.6 H.sub.3                                                                Br                                                                              H    CN   H                                            76  4-FC.sub.6 H.sub.4                                                                    2-Cl-4-FC.sub.6 H.sub.3                                                                Br                                                                              NO.sub.2                                                                           H    H                                            77  4-FC.sub.6 H.sub.4                                                                    2-Cl-4-FC.sub.6 H.sub.3                                                                Br                                                                              H    CH.sub.3                                                                           H                                            78  4-FC.sub.6 H.sub.4                                                                    2-FC.sub.6 H.sub.4                                                                     H Cl   Cl   H                                            79  4-FC.sub.6 H.sub.4                                                                    2-FC.sub.6 H.sub.4                                                                     H H    CO.sub.2 CH.sub.3                                                                  H                                            80  4-FC.sub.6 H.sub.4                                                                    2-FC.sub.6 H.sub.4                                                                     H Cl   CH.sub.3                                                                           H                                            81  4-FC.sub.6 H.sub.4                                                                    2-FC.sub.6 H.sub.4                                                                     Cl                                                                              Cl   Cl   H                                            82  4-FC.sub.6 H.sub.4                                                                    2-FC.sub.6 H.sub.4                                                                     Cl                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            83  4-FC.sub.6 H.sub.4                                                                    2-FC.sub.6 H.sub.4                                                                     Cl                                                                              Cl   CH.sub.3                                                                           H                                            84  4-FC.sub.6 H.sub.4                                                                    2-FC.sub.6 H.sub.4                                                                     Br                                                                              Cl   Cl   H                                            85  4-FC.sub.6 H.sub.4                                                                    2-FC.sub.6 H.sub.4                                                                     Br                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            86  4-FC.sub.6 H.sub.4                                                                    2-FC.sub.6 H.sub.4                                                                     Br                                                                              H    CH.sub.3                                                                           H                                            87  4-FC.sub.6 H.sub.4                                                                    4-FC.sub.6 H.sub.4                                                                     H Cl   Cl   H                                            88  4-FC.sub.6 H.sub.4                                                                    4-FC.sub.6 H.sub.4                                                                     H H    CO.sub.2 CH.sub.3                                                                  H                                            89  4-FC.sub.6 H.sub.4                                                                    4-FC.sub.6 H.sub.4                                                                     H Cl   CH.sub.3                                                                           H                                            90  4-FC.sub.6 H.sub.4                                                                    4-FC.sub.6 H.sub.4                                                                     H H    CH.sub.3                                                                           H                                            91  4-FC.sub.6 H.sub.4                                                                    4-FC.sub.6 H.sub.4                                                                     Cl                                                                              Cl   Cl   H                                            92  4-FC.sub.6 H.sub.4                                                                    4-FC.sub.6 H.sub.4                                                                     Cl                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            93  4-FC.sub.6 H.sub.4                                                                    4-FC.sub.6 H.sub.4                                                                     Cl                                                                              Cl   CH.sub.3                                                                           H                                            94  4-FC.sub.6 H.sub.4                                                                    4-FC.sub.6 H.sub.4                                                                     Cl                                                                              H    CH.sub.3                                                                           H                                            95  4-FC.sub.6 H.sub.4                                                                    4-FC.sub.6 H.sub.4                                                                     Br                                                                              Cl   Cl   H                                            96  4-FC.sub.6 H.sub.4                                                                    4-FC.sub.6 H.sub.4                                                                     Br                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            97  4-FC.sub.6 H.sub.4                                                                    4-FC.sub.6 H.sub.4                                                                     Br                                                                              Cl   CH.sub.3                                                                           H                                            98  4-FC.sub.6 H.sub.4                                                                    4-FC.sub.6 H.sub.4                                                                     Br                                                                              H    CH.sub.3                                                                           H                                            99  4-FC.sub.6 H.sub.4                                                                    2,4-F.sub.2C.sub.6 H.sub.3                                                             H Cl   Cl   H   resin      cis                           100 4-FC.sub.6 H.sub.4                                                                    2,4-F.sub.2C.sub.6 H.sub.3                                                             H H    CO.sub.2 CH.sub.3                                                                  H   141-144° C.                                                                       cis                           101 4-FC.sub.6 H.sub.4                                                                    2,4-F.sub.2C.sub.6 H.sub.3                                                             H Cl   CH.sub.3                                                                           H   144-147° C.                                                                       cis                           102 4-FC.sub.6 H.sub.4                                                                    2,4-F.sub.2C.sub.6 H.sub.3                                                             H H    COCH.sub.3                                                                         H   resin      cis                           103 4-FC.sub.6 H.sub.4                                                                    2,4-F.sub.2C.sub.6 H.sub.3                                                             H H    H    CH.sub.3                                     104 4-FC.sub.6 H.sub.4                                                                    2,4-F.sub.2C.sub.6 H.sub.3                                                             Cl                                                                              Cl   Cl   H   1607, 1507, 1463,                                                                        D.sub.1 :D.sub.2 = 2:1                                             1237, 964 cm.sup.-1                      105 4-FC.sub.6 H.sub.4                                                                    2,4-F.sub.2C.sub.6 H.sub.3                                                             Cl                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            106 4-FC.sub.6 H.sub.4                                                                    2,4-F.sub.2C.sub.6 H.sub.3                                                             Cl                                                                              Cl   CH.sub.3                                                                           H                                            107 4-FC.sub.6 H.sub.4                                                                    2,4-F.sub.2C.sub.6 H.sub.3                                                             Cl                                                                              H    CH.sub.3                                                                           H                                            108 4-FC.sub.6 H.sub.4                                                                    2,4-F.sub.2C.sub.6 H.sub.3                                                             Cl                                                                              H    H    CH.sub.3                                     109 4-FC.sub.6 H.sub.4                                                                    2,4-F.sub.2C.sub.6 H.sub.3                                                             Br                                                                              Cl   Cl   H                                            110 4-FC.sub.6 H.sub.4                                                                    2,4-F.sub.2C.sub.6 H.sub.3                                                             Br                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            111 4-FC.sub.6 H.sub.4                                                                    2,4-F.sub.2C.sub.6 H.sub.3                                                             Br                                                                              Cl   CH.sub.3                                                                           H                                            112 4-FC.sub.6 H.sub.4                                                                    2,6-F.sub.2C.sub.6 H.sub.3                                                             H Cl   Cl   H   131-132° C.                                                                       cis                           113 4-FC.sub.6 H.sub.4                                                                    2,6-F.sub.2C.sub.6 H.sub.3                                                             H H    CO.sub.2 CH.sub.3                                                                  H   resin      cis                           114 4-FC.sub.6 H.sub.4                                                                    2,6-F.sub.2C.sub.6 H.sub.3                                                             H Cl   CH.sub.3                                                                           H   129-132° C.                                                                       cis                           115 4-FC.sub.6 H.sub.4                                                                    2,6-F.sub.2C.sub.6 H.sub.3                                                             H H    COCH.sub.3                                                                         H   resin      cis                           116 4-FC.sub.6 H.sub.4                                                                    2,6-F.sub.2C.sub.6 H.sub.3                                                             Cl                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            117 4-FC.sub.6 H.sub.4                                                                    2,6-F.sub.2C.sub.6 H.sub.3                                                             Cl                                                                              Cl   CH.sub.3                                                                           H                                            118 4-FC.sub.6 H.sub.4                                                                    2,6-F.sub.2 C.sub.6 H.sub.3                                                            Br                                                                              Cl   Cl   H                                            119 4-FC.sub.6 H.sub.4                                                                    2,6-F.sub.2C.sub.6 H.sub.3                                                             Br                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            120 4-FC.sub.6 H.sub.4                                                                    2,6-F.sub.2C.sub.6 H.sub.3                                                             Br                                                                              H    H    CH.sub.3                                     121 4-FC.sub.6 H.sub.4                                                                    2,4-Cl.sub.2C.sub.6 H.sub.3                                                            H Cl   Cl   H                                            122 4-FC.sub.6 H.sub.4                                                                    2,4-Cl.sub.2C.sub.6 H.sub.3                                                            H H    CO.sub.2 CH.sub.3                                                                  H                                            123 4-FC.sub.6 H.sub.4                                                                    2,4-Cl.sub.2C.sub.6 H.sub.3                                                            H Cl   CH.sub.3                                                                           H                                            124 4-FC.sub.6 H.sub.4                                                                    2,4-Cl.sub.2C.sub.6 H.sub.3                                                            Cl                                                                              Cl   Cl   H                                            125 4-FC.sub.6 H.sub.4                                                                    2,4-Cl.sub.2C.sub.6 H.sub.3                                                            Cl                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            126 4-FC.sub.6 H.sub.4                                                                    2,4-Cl.sub.2C.sub.6 H.sub.3                                                            Cl                                                                              Cl   CH.sub.3                                                                           H                                            127 4-FC.sub.6 H.sub.4                                                                    2,4-Cl.sub.2C.sub.6 H.sub.3                                                            Br                                                                              Cl   Cl   H                                            128 4-FC.sub.6 H.sub.4                                                                    2,4-Cl.sub.2C.sub.6 H.sub.3                                                            Br                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            129 4-FC.sub.6 H.sub.4                                                                    2,4-Cl.sub.2C.sub.6 H.sub.3                                                            Br                                                                              Cl   CH.sub.3                                                                           H                                            130 4-FC.sub.6 H.sub.4                                                                    2-OCH.sub.3C.sub.6 H.sub.4                                                             H Cl   Cl   H                                            131 4-FC.sub.6 H.sub.4                                                                    2-OCH.sub.3C.sub.6 H.sub.4                                                             H H    CO.sub.2 CH.sub.3                                                                  H   1731, 1514, 1494,                                                                        cis                                                                1245, 1223, 758 cm.sup.-1                132 4-FC.sub.6 H.sub.4                                                                    2-OCH.sub.3C.sub.6 H.sub.4                                                             H Cl   CH.sub.3                                                                           H                                            133 4-FC.sub.6 H.sub.4                                                                    2-OCH.sub.3C.sub.6 H.sub.4                                                             H H    CH.sub.3                                                                           H                                            134 4-FC.sub.6 H.sub.4                                                                    2-OCH.sub.3C.sub.6 H.sub.4                                                             H H    H    CH.sub.3                                     135 4-FC.sub.6 H.sub.4                                                                    2-OCH.sub.3C.sub.6 H.sub.4                                                             H H    CN   H                                            136 4-FC.sub.6 H.sub.4                                                                    2-OCH.sub.3C.sub.6 H.sub.4                                                             H NO.sub.2                                                                           H    H                                            137 4-FC.sub.6 H.sub.4                                                                    2-OCH.sub.3C.sub.6 H.sub.4                                                             Cl                                                                              Cl   Cl   H   146-149° C.                                                                       cis                           138 4-FC.sub.6 H.sub.4                                                                    2-OCH.sub.3C.sub.6 H.sub.4                                                             Cl                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            139 4-FC.sub.6 H.sub.4                                                                    2-OCH.sub.3C.sub.6 H.sub.4                                                             Cl                                                                              Cl   CH.sub.3                                                                           H                                            140 4-FC.sub.6 H.sub.4                                                                    2-OCH.sub. 3C.sub.6 H.sub.4                                                            Cl                                                                              H    CH.sub.3                                                                           H                                            141 4-FC.sub.6 H.sub.4                                                                    2-OCH.sub.3C.sub.6 H.sub.4                                                             Cl                                                                              H    H    CH.sub.3                                     142 4-FC.sub.6 H.sub.4                                                                    2-OCH.sub.3C.sub.6 H.sub.4                                                             Cl                                                                              H    CN   H                                            143 4-FC.sub.6 H.sub.4                                                                    2-OCH.sub.3C.sub.6 H.sub.4                                                             Cl                                                                              NO.sub.2                                                                           H    H                                            144 4-FC.sub.6 H.sub.4                                                                    2-OCH.sub.3C.sub.6 H.sub.4                                                             Br                                                                              Cl   Cl   H   resin      D1:D2 = 3:1                   145 4-FC.sub.6 H.sub.4                                                                    2-OCH.sub.3C.sub.6 H.sub.4                                                             Br                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            146 4-FC.sub.6 H.sub.4                                                                    2-OCH.sub.3C.sub.6 H.sub.4                                                             Br                                                                              Cl   CH.sub.3                                                                           H                                            147 4-FC.sub.6 H.sub.4                                                                    4-OCF.sub.3C.sub.6 H.sub.4                                                             H Cl   Cl   H                                            148 4-FC.sub.6 H.sub.4                                                                    4-OCF.sub.3C.sub.6 H.sub.4                                                             H H    CO.sub.2 CH.sub.3                                                                  H                                            149 4-FC.sub.6 H.sub.4                                                                    4-OCF.sub.3C.sub.6 H.sub.4                                                             H Cl   CH.sub.3                                                                           H                                            150 4-FC.sub.6 H.sub.4                                                                    4-OCF.sub.3C.sub.6 H.sub.4                                                             H H    CH.sub.3                                                                           H                                            151 4-FC.sub.6 H.sub.4                                                                    4-OCF.sub.3C.sub.6 H.sub.4                                                             H H    H    CH.sub.3                                     152 4-FC.sub.6 H.sub.4                                                                    4-OCF.sub.3C.sub.6 H.sub.4                                                             H H    CN   H                                            153 4-FC.sub.6 H.sub.4                                                                    4-OCF.sub.3C.sub.6 H.sub.4                                                             Cl                                                                              Cl   Cl   H                                            154 4-FC.sub.6 H.sub.4                                                                    4-OCF.sub.3C.sub.6 H.sub.4                                                             Cl                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            155 4-FC.sub.6 H.sub.4                                                                    4-OCF.sub.3C.sub.6 H.sub.4                                                             Cl                                                                              Cl   CH.sub.3                                                                           H                                            156 4-FC.sub.6 H.sub.4                                                                    4-OCF.sub.3C.sub.6 H.sub.4                                                             Cl                                                                              H    CH.sub.3                                                                           H                                            157 4-FC.sub.6 H.sub.4                                                                    4-OCF.sub.3C.sub.6 H.sub.4                                                             Br                                                                              Cl   Cl   H                                            158 4-FC.sub.6 H.sub.4                                                                    4-OCF.sub.3C.sub.6 H.sub.4                                                             Br                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            159 4-FC.sub.6 H.sub.4                                                                    4-OCF.sub.3C.sub.6 H.sub.4                                                             Br                                                                              Cl   CH.sub.3                                                                           H                                            160 4-FC.sub.6 H.sub.4                                                                    4-OCF.sub.3C.sub.6 H.sub.4                                                             Br                                                                              H    CH.sub.3                                                                           H                                            161 4-FC.sub.6 H.sub.4                                                                    C.sub.6 H.sub.5                                                                        H Cl   Cl   H   125-128° C.                                                                       cis                           162 4-FC.sub.6 H.sub.4                                                                    C.sub.6 H.sub.5                                                                        H H    CO.sub.2 CH.sub.3                                                                  H   116-120° C.                                                                       cis                           163 4-F C.sub.6 H.sub.4                                                                   C.sub.6 H.sub.5                                                                        H Cl   CH.sub.3                                                                           H                                            164 4-FC.sub.6 H.sub.4                                                                    C.sub.6 H.sub.5                                                                        H H    CH.sub.3                                                                           H                                            165 4-FC.sub.6 H.sub.4                                                                    C.sub.6 H.sub.5                                                                        Cl                                                                              Cl   Cl   H                                            166 4-FC.sub.6 H.sub.4                                                                    C.sub.6 H.sub.5                                                                        Cl                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            167 4-FC.sub.6 H.sub.4                                                                    C.sub.6 H.sub.5                                                                        Cl                                                                              Cl   CH.sub.3                                                                           H                                            168 4-FC.sub.6 H.sub.4                                                                    C.sub.6 H.sub.5                                                                        Cl                                                                              H    CH.sub.3                                                                           H                                            169 4-FC.sub.6 H.sub.4                                                                    C.sub.6 H.sub.5                                                                        Br                                                                              Cl   Cl   H                                            170 4-FC.sub.6 H.sub.4                                                                    C.sub.6 H.sub.5                                                                        Br                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            171 4-FC.sub.6 H.sub.4                                                                    C.sub.6 H.sub.5                                                                        Br                                                                              Cl   CH.sub.3                                                                           H                                            172 4-FC.sub.6 H.sub.4                                                                    C.sub.6 H.sub.5                                                                        Br                                                                              H    CH.sub.3                                                                           H                                            173 4-FC.sub.6 H.sub.4                                                                    cyclohexyl                                                                             H Cl   Cl   H   2929, 1513, 1253,                                                                        cis                                                                837 cm.sup.-1                            174 4-FC.sub.6 H.sub.4                                                                    cyclohexyl                                                                             H H    CO.sub.2 CH.sub.3                                                                  H                                            175 4-FC.sub.6 H.sub.4                                                                    cyclohexyl                                                                             H Cl   CH.sub. 3                                                                          H                                            176 4-FC.sub.6 H.sub.4                                                                    cyclohexyl                                                                             Cl                                                                              Cl   Cl   H                                            177 4-FC.sub.6 H.sub.4                                                                    cyclohexyl                                                                             Cl                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            178 4-FC.sub.6 H.sub.4                                                                    cyclohexyl                                                                             Cl                                                                              Cl   CH.sub.3                                                                           H                                            179 4-FC.sub.6 H.sub.4                                                                    cyclohexyl                                                                             Br                                                                              Cl   Cl   H                                            180 4-FC.sub.6 H.sub.4                                                                    cyclohexyl                                                                             Br                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            181 C.sub.6 H.sub.5                                                                       2-ClC.sub.6 H.sub.4                                                                    H Cl   Cl   H   124-128° C.                                                                       cis                           182 C.sub.6 H.sub.5                                                                       2-ClC.sub.6 H.sub.4                                                                    H H    CO.sub.2 CH.sub.3                                                                  H   resin      cis                           183 C.sub.6 H.sub.5                                                                       2-ClC.sub.6 H.sub.4                                                                    H Cl   CH.sub.3                                                                           H   142° C.                                                                           cis                           184 C.sub.6 H.sub.5                                                                       2-ClC.sub.6 H.sub.4                                                                    H H    H    CH.sub.3                                                                          89-90° C.                                                                         cis                           185 C.sub.6 H.sub.5                                                                       2-ClC.sub.6 H.sub.4                                                                    H H    CN   H   105-110° C.                                                                       cis                           186 C.sub.6 H.sub.5                                                                       2-ClC.sub.6 H.sub.4                                                                    H NO.sub.2                                                                           H    H   200° C.                                                                           cis                           187 C.sub.6 H.sub.5                                                                       2-ClC.sub.6 H.sub.4                                                                    H H    CH.sub.3                                                                           H   91-95° C.                                                                         cis/trans =  1.5:1            188 C.sub.6 H.sub.5                                                                       2-ClC.sub.6 H.sub.4                                                                    Cl                                                                              Cl   Cl   H                                            189 C.sub.6 H.sub.5                                                                       2-ClC.sub.6 H.sub.4                                                                    Cl                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            190 C.sub.6 H.sub.5                                                                       2-ClC.sub.6 H.sub.4                                                                    Cl                                                                              Cl   CH.sub.3                                                                           H                                            191 C.sub.6 H.sub.5                                                                       2-ClC.sub.6 H.sub.4                                                                    Br                                                                              Cl   Cl   H                                            192 C.sub.6 H.sub.5                                                                       2-ClC.sub.6 H.sub.4                                                                    Br                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            193 C.sub.6 H.sub.5                                                                       C.sub.6 H.sub.5                                                                        H Cl   Cl   H                                            194 C.sub.6 H.sub.5                                                                       C.sub.6 H.sub.5                                                                        H H    CO.sub.2 CH.sub.3                                                                  H                                            195 C.sub.6 H.sub.5                                                                       C.sub.6 H.sub.5                                                                        Cl                                                                              Cl   Cl   H                                            196 C.sub.6 H.sub.5                                                                       C.sub.6 H.sub.5                                                                        Cl                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            197 C.sub.6 H.sub.5                                                                       C.sub.6 H.sub.5                                                                        Br                                                                              Cl   Cl   H                                            198 C.sub.6 H.sub.5                                                                       C.sub.6 H.sub.5                                                                        Br                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            199 C.sub.6 H.sub.5                                                                       4-ClC.sub.6 H.sub.4                                                                    H Cl   Cl   H                                            200 C.sub.6 H.sub.5                                                                       4-ClC.sub.6 H.sub.4                                                                    Cl                                                                              Cl   Cl   H                                            201 C.sub.6 H.sub.5                                                                       4-Cl C.sub.6 H.sub.4                                                                   Br                                                                              Cl   Cl   H                                            202 C.sub.6 H.sub.5                                                                       2,4-Cl.sub.2C.sub.6 H.sub.3                                                            H H    CO.sub.2 CH.sub.3                                                                  H                                            203 C.sub.6 H.sub.5                                                                       2,4-Cl.sub.2C.sub.6 H.sub.3                                                            Cl                                                                              Cl   Cl   H                                            204 C.sub.6 H.sub.5                                                                       2,4-Cl.sub.2C.sub.6 H.sub.3                                                            Br                                                                              Cl   CH.sub.3                                                                           H                                            205 C.sub.6 H.sub.5                                                                       4-NO.sub.2C.sub.6 H.sub.4                                                              H Cl   Cl   H                                            206 C.sub.6 H.sub.5                                                                       3-NO.sub.2C.sub.6 H.sub.4                                                              H H    CH.sub.3                                                                           H                                            207 C.sub.6 H.sub.5                                                                       cyclohexyl                                                                             H CH.sub.3                                                                           Cl   H                                            208 4-ClC.sub.6 H.sub.4                                                                   C.sub.6 H.sub.5                                                                        H Cl   Cl   H                                            209 4-ClC.sub.6 H.sub.4                                                                   C.sub.6 H.sub.5                                                                        Cl                                                                              Cl   Cl   H                                            210 4-ClC.sub.6 H.sub.4                                                                   C.sub.6 H.sub.5                                                                        Br                                                                              H    CH.sub.3                                                                           H                                            211 4-ClC.sub.6 H.sub.4                                                                   4-ClC.sub.6 H.sub.4                                                                    H Cl   Cl   H                                            212 4-ClC.sub.6 H.sub.4                                                                   4-ClC.sub.6 H.sub.4                                                                    Cl                                                                              Cl   Cl   H                                            213 4-ClC.sub.6 H.sub.4                                                                   4-ClC.sub.6 H.sub.4                                                                    Br                                                                              H    H    CH.sub.3                                     214 4-ClC.sub.6 H.sub.4                                                                   2,4-Cl.sub.2C.sub.6 H.sub.3                                                            H Cl   Cl   H                                            215 4-ClC.sub.6 H.sub.4                                                                   2,4-Cl.sub.2C.sub.6 H.sub.3                                                            Cl                                                                              Cl   Cl   H                                            216 4-ClC.sub.6 H.sub.4                                                                   4-FC.sub.6 H.sub.4                                                                     Cl                                                                              Cl   Cl   H                                            217 4-ClC.sub.6 H.sub.4                                                                   4-FC.sub.6 H.sub.4                                                                     H Cl   Cl   H                                            218 4-ClC.sub.6 H.sub.4                                                                   4-FC.sub.6 H.sub.4                                                                     Br                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            219 4-ClC.sub.6 H.sub.4                                                                   2-FC.sub.6 H.sub.4                                                                     H Cl   Cl   H                                            220 4-ClC.sub.6 H.sub.4                                                                   2-FC.sub.6 H.sub.4                                                                     Cl                                                                              Cl   Cl   H                                            221 2-ClC.sub.6 H.sub.4                                                                   2-ClC.sub.6 H.sub.4                                                                    H Cl   Cl   H                                            222 2-ClC.sub.6 H.sub.4                                                                   2-ClC.sub.6 H.sub.4                                                                    Cl                                                                              Cl   Cl   H                                            223 2-ClC.sub.6 H.sub.4                                                                   2-ClC.sub.6 H.sub.4                                                                    Br                                                                              H    CH.sub.3                                                                           H                                            224 2-ClC.sub.6 H.sub.4                                                                   2-FC.sub.6 H.sub.4                                                                     H Cl   Cl   H                                            225 2-ClC.sub.6 H.sub.4                                                                   2-FC.sub.6 H.sub.4                                                                     Cl                                                                              Cl   Cl   H                                            226 2-ClC.sub.6 H.sub.4                                                                   4-ClC.sub.6 H.sub.4                                                                    H Cl   Cl   H                                            227 2-ClC.sub.6 H.sub.4                                                                   4-ClC.sub.6 H.sub.4                                                                    Cl                                                                              Cl   Cl   H                                            228 2-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    H Cl   Cl   H   87-94° C.                                                                         cis:trans = 3:1               229 2-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    Cl                                                                              H    CH.sub.3                                                                           H                                            230 2-FC.sub.6 H.sub.4                                                                    4-FC.sub.6 H.sub.4                                                                     H Cl   Cl   H                                            231 2-FC.sub.6 H.sub.4                                                                    4-FC.sub.6 H.sub.4                                                                     Cl                                                                              Cl   Cl   H                                            232 2-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    H Cl   Cl   H                                            233 2-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    Cl                                                                              Cl   Cl   H                                            234 2,4-Cl.sub.2C.sub.6 H.sub.3                                                           2-ClC.sub.6 H.sub.4                                                                    H H    CH.sub.3                                                                           H                                            235 2,4-Cl.sub.2C.sub.6 H.sub.3                                                           2-ClC.sub.6 H.sub.4                                                                    Cl                                                                              Cl   Cl   H                                            236 2,4-Cl.sub.2C.sub.6 H.sub.3                                                           4-ClC.sub.6 H.sub.4                                                                    H H    H    CH.sub.3                                     237 2,4-Cl.sub.2C.sub.6 H.sub.3                                                           4-ClC.sub.6 H.sub.4                                                                    Cl                                                                              Cl   Cl   H                                            238 2,4-Cl.sub.2C.sub.6 H.sub.3                                                           2,4-Cl.sub.2C.sub.6 H.sub.3                                                            H Cl   Cl   H                                            239 2,4-Cl.sub.2C.sub.6 H.sub.3                                                           2,4-Cl.sub.2C.sub.6 H.sub.3                                                            Cl                                                                              Cl   Cl   H                                            240 2,4-Cl.sub.2C.sub.6 H.sub.3                                                           4-FC.sub.6 H.sub.4                                                                     H H    CO.sub.2 CH.sub.3                                                                  H                                            241 2,4-Cl.sub.2C.sub.6 H.sub.3                                                           4-FC.sub.6 H.sub.4                                                                     Br                                                                              Cl   CH.sub.3                                                                           H                                            242 cyclohexyl                                                                            C.sub.6 H.sub.5                                                                        H Cl   Cl   H                                            243 cyclohexyl                                                                            C.sub.6 H.sub.5                                                                        Cl                                                                              H    CN   H                                            244 cyclohexyl                                                                            C.sub.6 H.sub.5                                                                        Br                                                                              H    H    CH.sub.3                                     245 cyclohexyl                                                                            2-ClC.sub.6 H.sub.4                                                                    H Cl   Cl   H                                            246 cyclohexyl                                                                            2-ClC.sub.6 H.sub.4                                                                    Cl                                                                              Cl   Cl   H                                            247 cyclohexyl                                                                            2-ClC.sub.6 H.sub.4                                                                    Br                                                                              H    CH.sub.3                                                                           H                                            248 cyclohexyl                                                                            4-ClC.sub.6 H.sub.4                                                                    H Cl   Cl   H                                            249 cyclohexyl                                                                            4-ClC.sub.6 H.sub.4                                                                    Cl                                                                              Cl   Cl   H                                            250 cyclohexyl                                                                            2,4-Cl.sub.2C.sub.6 H.sub.3                                                            H H    CO.sub.2 CH.sub.3                                                                  H                                            251 cyclohexyl                                                                            2,4-Cl.sub.2C.sub.6 H.sub.3                                                            Cl                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            252 cyclohexyl                                                                            2-FC.sub.6 H.sub.4                                                                     H H    CH.sub.3                                                                           H                                            253 cyclohexyl                                                                            2-FC.sub.6 H.sub.4                                                                     Cl                                                                              NO.sub.2                                                                           H    H                                            254 cyclohexyl                                                                            4-FC.sub.6 H.sub.4                                                                     H Cl   Cl   H                                            255 cyclohexyl                                                                            4-FC.sub.6 H.sub.4                                                                     Cl                                                                              Cl   Cl   H                                            256 cyclohexyl                                                                            4-FC.sub.6 H.sub.4                                                                     Br                                                                              Cl   Cl   H                                            257 cyclohexyl                                                                            2-Cl-4-FC.sub.6 H.sub.3                                                                H H    CO.sub.2 CH.sub.3                                                                  H                                            258 cyclohexyl                                                                            2-Cl-4-FC.sub.6 H.sub.3                                                                Cl                                                                              Cl   Cl   H                                            259 cyclohexyl                                                                            2-Cl-4-FC.sub.6 H.sub.3                                                                Br                                                                              Cl   CH.sub.3                                                                           H                                            260 tert.-C.sub.4 H.sub.9                                                                 C.sub.6 H.sub.5                                                                        H H    H    CH.sub.3                                     261 tert.-C.sub.4 H.sub.9                                                                 C.sub.6 H.sub.5                                                                        Cl                                                                              Cl   Cl   H                                            262 tert.-C.sub.4 H.sub.9                                                                 2-ClC.sub.6 H.sub.4                                                                    H Cl   Cl   H                                            263 tert.-C.sub.4 H.sub.9                                                                 2-ClC.sub.6 H.sub.4                                                                    Cl                                                                              Cl   CH.sub.3                                                                           H                                            264 tert.-C.sub.4 H.sub.9                                                                 4-ClC.sub.6 H.sub.4                                                                    H Cl   Cl   H                                            265 tert.-C.sub.4 H.sub.9                                                                 4-ClC.sub.6 H.sub.4                                                                    H H    CO.sub.2 CH.sub.3                                                                  H                                            266 tert.-C.sub.4 H.sub.9                                                                 4-ClC.sub.6 H.sub.4                                                                    H Cl   CH.sub.3                                                                           H                                            267 tert.-C.sub.4 H.sub.9                                                                 4-ClC.sub.6 H.sub.4                                                                    H H    CH.sub.3                                                                           H                                            268 tert.-C.sub.4 H.sub.9                                                                 4-ClC.sub.6 H.sub.4                                                                    H H    H    CH.sub.3                                     269 tert.-C.sub.4 H.sub.9                                                                 4-ClC.sub.6 H.sub.4                                                                    Cl                                                                              Cl   Cl   H                                            270 tert.-C.sub.4 H.sub. 9                                                                4-ClC.sub.6 H.sub.4                                                                    Cl                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            271 tert.-C.sub.4 H.sub.9                                                                 4-ClC.sub.6 H.sub.4                                                                    Cl                                                                              Cl   CH.sub.3                                                                           H                                            272 tert.-C.sub.4 H.sub.9                                                                 4-ClC.sub.6 H.sub.4                                                                    Cl                                                                              H    CH.sub.3                                                                           H                                            273 tert.-C.sub.4 H.sub.9                                                                 4-ClC.sub.6 H.sub.4                                                                    Cl                                                                              H    H    CH.sub.3                                     274 tert.-C.sub.4 H.sub.9                                                                 4-ClC.sub.6 H.sub.4                                                                    Br                                                                              Cl   Cl   H                                            275 tert.-C.sub.4 H.sub.9                                                                 4-ClC.sub.6 H.sub.4                                                                    Br                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            276 tert.-C.sub.4 H.sub.9                                                                 4-ClC.sub.6 H.sub.4                                                                    Br                                                                              Cl   CH.sub.3                                                                           H                                            277 2,4-Cl.sub.2C.sub.6 H.sub.3                                                           2-ClC.sub.6 H.sub.4                                                                    H Cl   Cl   H                                            278 2,4-Cl.sub.2C.sub.6 H.sub.3                                                           2-ClC.sub.6 H.sub.4                                                                    Cl                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            279 2,4-Cl.sub.2C.sub.6 H.sub.3                                                           4-ClC.sub.6 H.sub.4                                                                    H Cl   Cl   H                                            280 2,4-Cl.sub.2C.sub.6 H.sub.3                                                           4-ClC.sub.6 H.sub.4                                                                    Cl                                                                              Cl   Cl   H                                            281 2,4-Cl.sub.2C.sub.6 H.sub.3                                                           2,4-Cl.sub.2C.sub.6 H.sub.3                                                            Cl                                                                              Cl   Cl   H                                            282 2,4-Cl.sub.2C.sub.6 H.sub.3                                                           2,4-Cl.sub.2C.sub.6 H.sub. 3                                                           H H    CH.sub.3                                                                           H                                            283 2,4-Cl.sub.2C.sub.6 H.sub.3                                                           4-FC.sub.6 H.sub.4                                                                     H Cl   CH.sub.3                                                                           H                                            284 2,4-Cl.sub.2C.sub.6 H.sub.3                                                           2-FC.sub.6 H.sub.4                                                                     H H    H    CH.sub.3                                     285 4-BrC.sub.6 H.sub.4                                                                   4-C(CH.sub.3).sub.3C.sub.6 H.sub.4                                                     H H    CH.sub.3                                                                           H                                            286 2-OCH.sub.3C.sub.6 H.sub.4                                                            2-ClC.sub.6 H.sub.4                                                                    H Cl   Cl   H                                            287 2-OCH.sub.3C.sub.6 H.sub.4                                                            4-ClC.sub.6 H.sub.4                                                                    Cl                                                                              H    CO.sub.2 CH.sub.3                                                                  H                                            288 2-OCH.sub.3C.sub.6 H.sub.4                                                            2-C.sub.10 H.sub.7                                                                     H Cl   Cl   H                                            289 2-OCH.sub.3C.sub.6 H.sub.4                                                            4-FC.sub.6 H.sub.4                                                                     H H    CO.sub.2 CH.sub.3                                                                  H                                            290 2-OCH.sub.3C.sub.6 H.sub.4                                                            2-FC.sub.6 H.sub.4                                                                     H Cl   Cl   H                                            291 2-C.sub.10 H.sub.7                                                                    2-ClC.sub.6 H.sub.4                                                                    H Cl   Cl   H                                            292 2-C.sub.10 H.sub.7                                                                    4-FC.sub.6 H.sub.4                                                                     Cl                                                                              Cl   Cl   H                                            293 4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    H H    COCH.sub.3                                                                         CH.sub.3                                                                          130-131° C.                                                                       cis                           294 4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    Cl                                                                              H    COCH.sub.3                                                                         CH.sub.3                                     295 4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    Br                                                                              H    COCH.sub.3                                                                         CH.sub.3                                     296 4-FC.sub.6 H.sub.4                                                                    2-CF.sub.3C.sub.6 H.sub.4                                                              F Cl   Cl   H                                            297 4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    F Cl   CH.sub.3                                                                           H                                            298 4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    F Cl   Cl   H                                            299 4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    F H    CN   H                                            300 4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    F Cl   Cl   H                                            301 4-FC.sub.6 H.sub.4                                                                    4-ClC.sub.6 H.sub.4                                                                    F Cl   CH.sub.3                                                                           H                                            302 4-FC.sub.6 H.sub.4                                                                    2-Cl-4-FC.sub.6 H.sub.3                                                                F Cl   Cl   H                                            303 4-FC.sub.6 H.sub.4                                                                    2-FC.sub.6 H.sub.4                                                                     F H    CN   H                                            304 4-FC.sub.6 H.sub.4                                                                    4-FC.sub.6 H.sub.4                                                                     F Cl   CH.sub.3                                                                           H                                            305 4-FC.sub.6 H.sub.4                                                                    2,4-F.sub.2C.sub.6 H.sub.3                                                             F Cl   Cl   H                                            306 4-FC.sub.6 H.sub.4                                                                    2,6-F.sub.2C.sub.6 H.sub.3                                                             F Cl   Cl   H                                            307 4-FC.sub.6 H.sub.4                                                                    2,4-Cl.sub.2C.sub.6 H.sub.3                                                            F H    COCH.sub.3                                                                         CH.sub.3                                     308 4-FC.sub.6 H.sub.4                                                                    2-OCH.sub.3C.sub.6 H.sub.4                                                             F Cl   Cl   H                                            309 4-FC.sub.6 H.sub.4                                                                    4-OCH.sub.3C.sub.6 H.sub.4                                                             F H    CN   H                                            310 4-FC.sub.6 H.sub.4                                                                    C.sub.6 H.sub.5                                                                        F Cl   CH.sub.3                                                                           H                                            311 4-FC.sub.6 H.sub.4                                                                    cyclohexyl                                                                             F Cl   Cl   H                                            312 C.sub.6 H.sub.5                                                                       4-ClC.sub.6 H.sub.4                                                                    F Cl   Cl   H                                            313 4-ClC.sub.6 H.sub.4                                                                   4-ClC.sub.6 H.sub.4                                                                    F Cl   CH.sub.3                                                                           H                                            314 cyclohexyl                                                                            4-FC.sub.6 H.sub.4                                                                     F Cl   Cl   H                                            315 4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    H H    COCH.sub.3                                                                         H   resin      cis                           316 4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    H COCH.sub.3                                                                         CH.sub.3                                                                           H   136-141° C.                                                                       cis                           317 4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    H H    phenyl                                                                             H   resin      D1:D2 = 2:1                   318 4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    H H    H    phenyl                                       319 4-FC.sub.6 H.sub.4                                                                    C.sub.6 H.sub. 5                                                                       H H    CN   H   126-130° C.                                                                       cis                           320 4-FC.sub.6 H.sub.4                                                                    2-F-3ClC.sub.6 H.sub.3                                                                 H Cl   Cl   H   150-153° C.                                                                       cis                           321 4-FC.sub.6 H.sub.4                                                                    4-OCF.sub.3C.sub.6 H.sub.4                                                             H H    CO.sub.2 CH.sub.3                                                                  H   resin      cis                           322 C.sub.6 H.sub.5                                                                       2-OCH.sub.3C.sub.6 H.sub.4                                                             H Cl   Cl   H   resin      cis                           323 4-FC.sub.6 H.sub.4                                                                    2-BrC.sub.6 H.sub.4                                                                    H H    CO.sub.2 CH.sub.3                                                                  H   resin      cis                           324 4-FC.sub.6 H.sub.4                                                                    2-ClC.sub.6 H.sub.4                                                                    H CO.sub.2 CH.sub.3                                                                  CO.sub.2 CH.sub.3                                                                  H   134-140° C.                                                                       cis                           __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________     ##STR17##                                                                    Ex. R.sup.1                                                                              R.sup.2 E X  Y    Z  m.p./IR   Isomer                              __________________________________________________________________________     1a 4-FC.sub.6 H.sub.4                                                                   2-ClC.sub.6 H.sub.4                                                                   H NO.sub.2                                                                         H    H  161-165° C.                                                                      Z                                    2a 4-FC.sub.6 H.sub.4                                                                   2-ClC.sub.6 H.sub.4                                                                   H H  CO.sub.2 CH.sub.3                                                                  H  132-135° C.                                                                      Z                                    3a 4-FC.sub.6 H.sub.4                                                                   2-ClC.sub.6 H.sub.4                                                                   H Cl Cl   H   84-89° C.                                                                       Z                                    4a 4-FC.sub.6 H.sub.4                                                                   2-ClC.sub.6 H.sub.4                                                                   H H  CN   H   99-108° C.                                                                      Z/E = 6:1                            5a 4-FC.sub.6 H.sub.4                                                                   2-ClC.sub.6 H.sub.4                                                                   H Cl CH.sub.3                                                                           H  resin     Z/E = 3:2                            6a 4-FC.sub.6 H.sub.4                                                                   2-Cl C.sub.6 H.sub.4                                                                  H H  H    CH.sub.3                                                                         1603, 1509, 1228                                                                        Z                                                                   846, 830, 759 cm.sup.-1                        7a 4-FC.sub.6 H.sub.4                                                                   2-ClC.sub.6 H.sub.4                                                                   H H  CH.sub.3                                                                           H   93-95° C.                                                                       Z                                    8a 4-FC.sub.6 H.sub.4                                                                   2-ClC.sub.6 H.sub.4                                                                   Cl                                                                              Cl Cl   H  1603, 1510, 1470,                                                                       E                                                                   1233, 847, 753 cm.sup.-1                       9a 4-FC.sub.6 H.sub.4                                                                   2-ClC.sub.6 H.sub.4                                                                   Cl                                                                              Cl CH.sub.3                                                                           H                                                10a 4-FC.sub.6 H.sub.4                                                                   2-ClC.sub.6 H.sub.4                                                                   Br                                                                              Cl Cl   H  172-175° C.                                                                      E                                   11a 4-FC.sub.6 H.sub.4                                                                   2-ClC.sub.6 H.sub.4                                                                   Br                                                                              Cl CH.sub.3                                                                           H                                                12a 4-FC.sub.6 H.sub.4                                                                   4-ClC.sub.6 H.sub.4                                                                   H Cl Cl   H                                                13a 4-FC.sub.6 H.sub.4                                                                   4-ClC.sub.6 H.sub.4                                                                   Cl                                                                              Cl Cl   H                                                14a 4-FC.sub.6 H.sub.4                                                                   4-ClC.sub.6 H.sub.4                                                                   Br                                                                              Cl Cl   H                                                15a 4-FC.sub.6 H.sub.4                                                                   2,4-Cl.sub.2C.sub.6 H.sub.3                                                           H H  CO.sub.2 CH.sub.3                                                                  H                                                16a 4-FC.sub.6 H.sub.4                                                                   2,4-Cl.sub.2C.sub.6 H.sub.3                                                           Cl                                                                              H  CO.sub.2 CH.sub.3                                                                  H                                                17a 4-FC.sub.6 H.sub.4                                                                   2,4-Cl.sub.2C.sub.6 H.sub.3                                                           Br                                                                              H  CO.sub.2 CH.sub.3                                                                  H                                                18a 4-FC.sub.6 H.sub.4                                                                   2-Cl-4-FC.sub.6 H.sub.3                                                               H Cl Cl   H                                                19a 4-FC.sub.6 H.sub.4                                                                   2-Cl-4-FC.sub.6 H.sub.3                                                               Cl                                                                              Cl Cl   H                                                20a 4-FC.sub.6 H.sub.4                                                                   2-Cl-4-FC.sub.6 H.sub.3                                                               Br                                                                              Cl Cl   H                                                21a 4-FC.sub.6 H.sub.4                                                                   2-CF.sub.3C.sub.6 H.sub.4                                                             H NO.sub.2                                                                         H    H                                                22a 4-FC.sub.6 H.sub.4                                                                   2-CF.sub.3C.sub.6 H.sub.4                                                             H H  CO.sub.2 CH.sub.3                                                                  H                                                23a 4-FC.sub.6 H.sub.4                                                                   2-CF.sub.3C.sub.6 H.sub.4                                                             H Cl Cl   H  1604, 1561, 1316,                                                                       E/Z = 2:1                                                           1126, 768 cm.sup.-1                           24a 4-FC.sub.6 H.sub.4                                                                   2-CF.sub.3C.sub.6 H.sub.4                                                             H H  CN   H                                                25a 4-FC.sub.6 H.sub.4                                                                   2-CF.sub.3C.sub.6 H.sub.4                                                             H Cl CH.sub.3                                                                           H  1510, 1316, 1167                                                                        E/ = 2:1                                                            1123, 769 cm.sup.-1                           26a 4-FC.sub.6 H.sub.4                                                                   2-CF.sub.3C.sub.6 H.sub.4                                                             H H  H    CH.sub.3                                         27a 4-FC.sub.6 H.sub.4                                                                   2-CF.sub.3C.sub.6 H.sub.4                                                             H H  CH.sub.3                                                                           H                                                28a 4-FC.sub.6 H.sub.4                                                                   2-CF.sub.3C.sub.6 H.sub.4                                                             Cl                                                                              Cl Cl   H                                                29a 4-FC.sub.6 H.sub.4                                                                   2-CF.sub.3C.sub.6 H.sub.4                                                             Cl                                                                              H  CO.sub.2 CH.sub.3                                                                  H                                                30a 4-FC.sub.6 H.sub.4                                                                   2-CF.sub.3C.sub.6 H.sub.4                                                             Cl                                                                              Cl CH.sub.3                                                                           H                                                31a 4-FC.sub.6 H.sub.4                                                                   2-CF.sub.3C.sub.6 H.sub.4                                                             Br                                                                              Cl Cl   H                                                32a 4-FC.sub.6 H.sub.4                                                                   2-CF.sub.3C.sub.6 H.sub.4                                                             Br                                                                              Cl CH.sub.3                                                                           H                                                33a 4-FC.sub.6 H.sub.4                                                                   2-CF.sub.3C.sub.6 H.sub.4                                                             Br                                                                              H  CO.sub.2 CH.sub.3                                                                  H                                                34a 4-FC.sub.6 H.sub.4                                                                   4-CF.sub.3C.sub.6 H.sub.4                                                             H Cl Cl   H                                                35a 4-FC.sub.6 H.sub.4                                                                   4-CF.sub.3C.sub.6 H.sub.4                                                             Cl                                                                              H  CO.sub.2 CH.sub.3                                                                  H                                                36a 4-FC.sub.6 H.sub.4                                                                   4-CF.sub.3C.sub.6 H.sub.4                                                             Br                                                                              Cl CH.sub.3                                                                           H                                                37a 4-FC.sub.6 H.sub. 4                                                                  2-FC.sub.6 H.sub.4                                                                    H Cl Cl   H                                                38a 4-FC.sub.6 H.sub.4                                                                   2-FC.sub.6 H.sub.4                                                                    H Cl CH.sub.3                                                                           H                                                39a 4-FC.sub.6 H.sub.4                                                                   2-FC.sub.6 H.sub.4                                                                    Cl                                                                              Cl Cl   H                                                40a 4-FC.sub.6 H.sub.4                                                                   2-FC.sub.6 H.sub.4                                                                    Cl                                                                              H  CO.sub.2 CH.sub.3                                                                  H                                                41a 4-FC.sub.6 H.sub.4                                                                   2-FC.sub.6 H.sub.4                                                                    Br                                                                              Cl Cl   H                                                42a 4-FC.sub.6 H.sub.4                                                                   2-FC.sub.6 H.sub.4                                                                    Br                                                                              Cl CH.sub.3                                                                           H                                                43a 4-FC.sub.6 H.sub.4                                                                   4-FC.sub.6 H.sub.4                                                                    H Cl Cl   H                                                44a 4-FC.sub.6 H.sub.4                                                                   4-FC.sub.6 H.sub.4                                                                    H H  CO.sub.2 CH.sub.3                                                                  H                                                45a 4-FC.sub.6 H.sub.4                                                                   4-FC.sub.6 H.sub.4                                                                    Cl                                                                              Cl Cl   H                                                46a 4-FC.sub.6 H.sub.4                                                                   4-FC.sub.6 H.sub.4                                                                    Cl                                                                              H  CO.sub.2 CH.sub.3                                                                  H                                                47a 4-FC.sub.6 H.sub.4                                                                   4-FC.sub.6 H.sub.4                                                                    Br                                                                              Cl Cl   H                                                48a 4-FC.sub.6 H.sub.4                                                                   4-ClC.sub.6 H.sub.4                                                                   Br                                                                              H  CO.sub.2 CH.sub.3                                                                  H                                                49a 4-FC.sub.6 H.sub.4                                                                   2,4-F.sub.2C.sub.6 H.sub. 3                                                           H Cl Cl   H                                                50a 4-FC.sub.6 H.sub.4                                                                   2,4-F.sub.2C.sub.6 H.sub.3                                                            H H  CO.sub.2 CH.sub.3                                                                  H                                                51a 4-FC.sub.6 H.sub.4                                                                   2,4-F.sub.2C.sub.6 H.sub.3                                                            Cl                                                                              Cl Cl   H                                                52a 4-FC.sub.6 H.sub.4                                                                   2,4-F.sub.2C.sub.6 H.sub.3                                                            Cl                                                                              H  CO.sub.2 CH.sub.3                                                                  H                                                53a 4-FC.sub.6 H.sub.4                                                                   2,4-F.sub.2C.sub.6 H.sub.3                                                            Br                                                                              Cl Cl   H                                                54a 4-FC.sub.6 H.sub.4                                                                   2,4-F.sub.2C.sub.6 H.sub.3                                                            Br                                                                              H  CO.sub.2 CH.sub.3                                                                  H                                                55a 4-FC.sub.6 H.sub.4                                                                   2,6-F.sub.2C.sub.6 H.sub.3                                                            H Cl Cl   H                                                56a 4-FC.sub.6 H.sub.4                                                                   2,6-F.sub.2C.sub.6 H.sub.3                                                            H H  CO.sub.2 CH.sub.3                                                                  H                                                57a 4-FC.sub.6 H.sub.4                                                                   2,6-F.sub.2C.sub.6 H.sub.3                                                            Cl                                                                              Cl Cl   H                                                58a 4-FC.sub.6 H.sub.4                                                                   2,6-F.sub.2C.sub.6 H.sub.3                                                            Cl                                                                              H  CO.sub.2 CH.sub.3                                                                  H                                                59a 4-FC.sub.6 H.sub.4                                                                   2,6-F.sub.2C.sub.6 H.sub.3                                                            Br                                                                              Cl Cl   H                                                60a 4-FC.sub.6 H.sub.4                                                                   2,6-F.sub.2C.sub.6 H.sub.3                                                            Br                                                                              H  CO.sub.2 CH.sub.3                                                                  H                                                61a 4-FC.sub.6 H.sub.4                                                                   2-OCH.sub.3C.sub.6 H.sub.4                                                            H Cl Cl   H  resin     E/Z = 3:1                           62a 4-FC.sub.6 H.sub.4                                                                   2-OCH.sub.3C.sub.6 H.sub.4                                                            H Cl CH.sub.3                                                                           H  1599, 1509,                                                                             E/Z = 3:1                                                           1248, 1225,                                                                   754 cm.sup.-1                                 63a 4-FC.sub.6 H.sub.4                                                                   2-OCH.sub.3C.sub.6 H.sub.4                                                            H H  CN   H  resin     E/Z = 3:1                           64a 4-FC.sub.6 H.sub.4                                                                   2-OCH.sub.3C.sub.6 H.sub.4                                                            H H  CH.sub.3                                                                           H  1599, 1509, 1247,                                                                       E/Z = 3:1                                                           754 cm.sup.-1                                 65a 4-FC.sub.6 H.sub.4                                                                   2-OCH.sub.3C.sub.6 H.sub.4                                                            H H  CO.sub.2 CH.sub.3                                                                  H  1720, 1509, 1248,                                                                       E/Z = 3:1                                                           1116, 755 cm.sup.-1                           66a 4-FC.sub.6 H.sub.4                                                                   2-OCH.sub.3C.sub.6 H.sub.4                                                            Cl                                                                              Cl Cl   H                                                67a 4-FC.sub.6 H.sub.4                                                                   2-OCH.sub.3C.sub.6 H.sub.4                                                            Br                                                                              H  CO.sub.2 CH.sub.3                                                                  H                                                68a 4-FC.sub.6 H.sub.4                                                                   4-OCF.sub.3 C.sub.6 H.sub.4                                                           H Cl Cl   H                                                69a 4-FC.sub.6 H.sub.4                                                                   4-OCF.sub.3C.sub.6 H.sub.4                                                            Cl                                                                              Cl Cl   H                                                70a 4-FC.sub.6 H.sub.4                                                                   4-OCF.sub.3C.sub.6 H.sub.4                                                            Br                                                                              Cl Cl   H                                                71a 4-FC.sub.6 H.sub.4                                                                   C.sub.6 H.sub.5                                                                       H Cl Cl   H                                                72a 4-FC.sub.6 H.sub.4                                                                   C.sub.6 H.sub.5                                                                       Cl                                                                              H  CO.sub.2 CH.sub.3                                                                  H                                                73a 4-FC.sub.6 H.sub.4                                                                   cyclohexyl                                                                            H Cl Cl   H                                                74a 4-FC.sub.6 H.sub.4                                                                   cyclohexyl                                                                            Cl                                                                              H  CH.sub.3                                                                           H                                                75a C.sub.6 H.sub.5                                                                      C.sub.6 H.sub.5                                                                       H Cl Cl   H                                                76a C.sub.6 H.sub.5                                                                      C.sub.6 H.sub.5                                                                       Cl                                                                              H  H    CH.sub.3                                         77a C.sub.6 H.sub.5                                                                      C.sub.6 H.sub.5                                                                       Br                                                                              H  CO.sub.2 CH.sub.3                                                                  H                                                78a C.sub.6 H.sub.5                                                                      4-ClC.sub.6 H.sub.4                                                                   H Cl Cl   H                                                79a C.sub.6 H.sub.5                                                                      2-ClC.sub.6 H.sub.4                                                                   Cl                                                                              Cl Cl   H                                                80a C.sub.6 H.sub.5                                                                      2,4-Cl.sub.2C.sub.6 H.sub.3                                                           Br                                                                              H  CO.sub.2 CH.sub.3                                                                  H                                                81a C.sub.6 H.sub.5                                                                      4-FC.sub.6 H.sub.4                                                                    H Cl Cl   H                                                82a C.sub.6 H.sub.5                                                                      2-FC.sub.6 H.sub.4                                                                    H Cl Cl   H                                                83a 4-ClC.sub.6 H.sub.4                                                                  C.sub.6 H.sub.5                                                                       H Cl Cl   H                                                84a 4-ClC.sub.6 H.sub.4                                                                  2-ClC.sub.6 H.sub.4                                                                   H Cl Cl   H                                                85a 4-ClC.sub.6 H.sub.4                                                                  2-ClC.sub.6 H.sub.4                                                                   Cl                                                                              Cl Cl   H                                                86a 4-ClC.sub.6 H.sub.4                                                                  2,4-Cl.sub.2C.sub.6 H.sub.3                                                           Br                                                                              H  CH.sub.3                                                                           H                                                87a 4-ClC.sub.6 H.sub.4                                                                  4-FC.sub.6 H.sub.4                                                                    H Cl Cl   H                                                88a 4-ClC.sub.6 H.sub.4                                                                  2-FC.sub.6 H.sub.4                                                                    H Cl Cl   H                                                89a 2-ClC.sub.6 H.sub.4                                                                  2-ClC.sub.6 H.sub.4                                                                   H Cl Cl   H                                                90a 2-ClC.sub.6 H.sub.4                                                                  2-FC.sub.6 H.sub.4                                                                    H Cl Cl   H                                                91a 2-FC.sub.6 H.sub.4                                                                   2-FC.sub.6 H.sub.4                                                                    H Cl Cl   H                                                92a 2-FC.sub.6 H.sub.4                                                                   2-FC.sub.6 H.sub.4                                                                    H Cl Cl   H                                                93a 2-FC.sub.6 H.sub.4                                                                   4-FC.sub.6 H.sub.4                                                                    Br                                                                              Cl Cl   H                                                94a 2-FC.sub.6 H.sub.4                                                                   4-FC.sub.6 H.sub.4                                                                    H Cl Cl   H                                                95a cyclohexyl                                                                           2-ClC.sub.6 H.sub.4                                                                   H Cl Cl   H                                                96a cyclohexyl                                                                           4-ClC.sub.6 H.sub.4                                                                   Cl                                                                              Cl Cl   H                                                97a cyclohexyl                                                                           4-FC.sub.6 H.sub.4                                                                    H Cl Cl   H                                                98a 4-FC.sub.6 H.sub.4                                                                   2-ClC.sub.6 H.sub.4                                                                   F CH.sub.3                                                                         Cl   H                                                99a 4-FC.sub.6 H.sub.4                                                                   2-ClC.sub.6 H.sub.4                                                                   F Cl Cl   H                                                100a                                                                              4-FC.sub.6 H.sub.4                                                                   4-ClC.sub.6 H.sub.4                                                                   F H  CN   H                                                101a                                                                              4-FC.sub.6 H.sub.4                                                                   2,4-Cl.sub.2C.sub.6 H.sub.3                                                           F H  CN   H                                                102a                                                                              4-FC.sub.6 H.sub.4                                                                   2-Cl-4-FC.sub.6 H.sub.3                                                               F Cl Cl   H                                                103a                                                                              4-FC.sub.6 H.sub.4                                                                   2-CF.sub.3C.sub.6 H.sub.4                                                             F CH.sub.3                                                                         Cl   H                                                104a                                                                              4-FC.sub.6 H.sub.4                                                                   4-CF.sub.3C.sub.6 H.sub.4                                                             F Cl Cl   H                                                105a                                                                              4-FC.sub.6 H.sub.4                                                                   2-FC.sub.6 H.sub.4                                                                    F H  CH.sub.3                                                                           H                                                106a                                                                              4-FC.sub.6 H.sub.4                                                                   4-FC.sub.6 H.sub.4                                                                    F Cl Cl   H                                                107a                                                                              4-FC.sub.6 H.sub.4                                                                   2,4-F.sub.2C.sub.6 H.sub.3                                                            F H  CO.sub.2 CH.sub.3                                                                  H                                                108a                                                                              4-FC.sub.6 H.sub.4                                                                   2-OCH.sub.3C.sub.6 H.sub.3                                                            F H  CO.sub.2 CH.sub.3                                                                  H                                                109a                                                                              4-FC.sub.6 H.sub.4                                                                   4-OCF.sub.3C.sub.6 H.sub.4                                                            F Cl Cl   H                                                110a                                                                              C.sub.6 H.sub.5                                                                      4-ClC.sub.6 H.sub.4                                                                   F Cl Cl   H                                                __________________________________________________________________________

Generally speaking, the novel compounds are extremely effective on abroad spectrum of phytopathogenic fungi, in particular those from theAscomycetes and Basidiomycetes classes. Some of them have a systemicaction and can be used as foliar and soil fungicides.

The fungicidal compounds are of particular interest for controlling alarge number of fungi in various crops or their seeds, especially wheat,rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee,sugar cane, fruit and ornamentals in horticulture and viticulture, andin vegetables such as cucumbers, beans and cucurbits.

The novel compounds are particularly useful for controlling thefollowing plant diseases:

Erysiphe graminin in cereals,

Perysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,

Podosphaera leucotricha in apples,

Uncinula necator in vines,

Puccinia species in cereals,

Rhizoctonia species in cotton and lawns,

Ustilago species in cereals and sugar cane,

Venturia inaequalis (scab) in apples,

Helminthosporium species in cereals,

Septoria nodorum in wheat,

Botrytis cinerea (gray mold) in strawberries and grapes,

Cercospora arachidicola in groundnuts,

Pseudocercosporella herpotrichoides in wheat and barley,

Pyricularia oryzae in rice,

Phytophthora infestans in potatoes and tomatoes,

Fusarium and Verticillium species in various plants,

Plasmopara viticola in grapes,

Alternaria species in fruit and vegetables.

The compounds are applied by spraying or dusting the plants with theactive ingredients, or treating the seeds of the plants with the activeingredients. They may be applied before or after infection of the plantsor seeds by the fungi.

The novel substances can be converted into conventional formulationssuch as solutions, emulsions, suspensions, dusts, powders, pastes andgranules. The application forms depend entirely on the purposes forwhich they are intended; they should at all events ensure a fine anduniform distribution of the active ingredient. The formulations areproduced in known manner, for example by extending the active ingredientwith solvents and/or carriers, with or without the use of emulsifiersand dispersants; if water is used as solvent, it is also possible toemploy other organic solvents as auxiliary solvents. Suitableauxiliaries for this purpose are solvents such as aromatics (e.g.,xylene), chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g.,crude oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g.,cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), andwater; carriers such as ground natural minerals (e.g., kaolins,aluminas, talc and chalk) and ground synthetic minerals (e.g., highlydisperse silica and silicates); emulsifiers such as nonionic and anionicemulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkylsulfonates and aryl sulfonates); and dispersants such as lignin, sulfitewaste liquors and methylcellulose.

The fungicidal agents generally contain from 0.1 to 95, and preferablyfrom 0.5 to 90, wt % of active ingredient. The application rates arefrom 0.02 to 3 kg or more of active ingredient per hectare, depending onthe type of effect desired. The novel compounds may also be used forprotecting materials, for example against Paecilomyces variotii.

The agents and the ready-to-use formulations prepared from them such assolutions, emulsions, suspensions, powders, dusts, pastes and granules,are applied in conventional manner, for example by spraying, atomizing,dusting, scattering, dressing or watering.

Examples of formulations are given below.

I. 90 parts by weight of compound no. 113 is mixed with 10 parts byweight of N-methyl-α-pyrrolidone. A mixture is obtained which issuitable for application in the form of very fine drops.

II. 20 parts by weight of compound no. 115 is dissolved in a mixtureconsisting of 80 parts by weight of xylene, 10 parts by weight of theadduct of 8 to 10 moles of ethylene oxide and 1 mole of oleicacid-N-monethanolamide, 5 parts by weight of the calcium salt ofdodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40moles of ethylene oxide and 1 mole of castor oil. By pouring thesolution into water and uniformly distributing it therein, an aqueousdispersion is obtained.

III. 20 parts by weight of compound no 113 is dissolved in a mixtureconsisting of 40 parts by weight of cyclohexanone, 30 parts by weight ofisobutanol, 20 parts by weight of the adduct of 40 moles of ethyleneoxide and 1 mole of castor oil. By pouring the solution into water andfinely distributing it therein, an aqueous dispersion is obtained.

IV. 20 parts by weight of compound no 115 is dissolved in a mixtureconsisting of 25 parts by weight of cyclohexanol, 65 parts by weight ofa mineral oil fraction having a boiling point between 210° and 280° C.,and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1mole of castor oil. By pouring the solution into water and uniformlydistributing it therein, an aqueous dispersion is obtained.

V. 80 parts by weight of compound no. 113 is well mixed with 3 parts byweight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 10parts by weight of the sodium salt of a lignin-sulfonic acid obtainedfrom a sulfite waste liquor, and 7 parts by weight of powdered silicagel, and triturated in a hammer mill. By uniformly distributing themixture in water, a spray liquor is obtained.

VI. 3 parts by weight of compound no. 115 is intimately mixed with 97parts by weight of particulate kaolin. A dust is obtained containing 3%by weight of the active ingredient.

VII. 30 parts by weight of compound no. 113 is intimately mixed with amixture consisting of 92 parts by weight of powdered silica gel and 8parts by weight of paraffin oil which has been sprayed onto the surfaceof this silica gel. A formulation of the active ingredient is obtainedhaving good adherence.

VIII. 40 parts by weight of compound no. 115 is intimately mixed with 10parts of the sodium salt of a phenolsulfonic acid-urea-formaldehydecondensate, 2 parts of silica gel and 48 parts of water to give a stableaqueous dispersion. Dilution in water gives an aqueous dispersion.

IX. 20 parts by weight of compound no. 113 is intimately mixed with 2parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8parts by weight of a fatty alcohol polyglycol ethr, 2 parts by weight ofthe sodium salt of a phenolsulfonic acid-urea-formaldehyde condensateand 68 parts by weight of a paraffinic mineral oil. A stable oilydispersion is obtained.

In these application forms, the agents according to the invention mayalso be present together with other active ingredients, for exampleherbicides, insecticides, growth regulators, and fungicides, and mayfurthermore be mixed and applied together with fertilizers. Admixturewith other fungicides frequently results in an increase in thefungicidal spectrum.

The following list of fungicides with which the novel compounds may becombined is intended to illustrate possible combinations but not toimpose any restrictions.

Examples of fungicides which may be combined with the novel compoundsare;

sulfur,

dithiocarbamates and their derivatives, such as

ferric dimethyldithiocarbamate,

zinc dimethyldithiocarbamate,

zinc ethylenebisdithiocarbamate,

manganese ethylenebisdithiocarbamate,

manganese zinc ethylenediaminebisdithiocarbamate,

tetramethylthiuram disulfides,

ammonia complex of zinc N,N'-ethylenebisdithiocarbamate,

ammonia complex of zinc N,N'-propylenebisdithiocarbamate,

zinc N,N'-propylenebisdithiocarbamate and

N,N'-polypropylenebis(thiocarbamyl) disulfide;

nitro derivatives, such as

dinitro(1-methylheptyl)-phenyl crotonate,

2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate,

2-sec-butyl-4,6-dinitrophenyl isopropylcarbonate and

diisopropyl 5-nitroisophthalate;

heterocyclic substances, such as

2-heptadecylimidazol-2-yl acetate,

2,4-dichloro-6-(o-chloroanilino)-s-triazine,

O,O-diethyl phthalimidophosphonothiote,

5-amino-1-[-bis-(dimethylamino)-phosphinyl]-3-phenyl-1,2,4-triazole,

2,3-dicyano-1,4-dithioanthraquinone,

2-thio-1,3-dithio[4,5-b]quinoxaline,

methyl 1-(butylcarbamyl)-2-benzimidazolecarbamate,

2-methoxycarbonylaminobenzimidazole,

2-(fur-2-yl)-benzimidazole,

2-(thiazol-4-yl)benzimidazole,

N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide,

N-trichloromethylthiotetrahydrophthalimide,

N-trichloromethylthiophthalimide,

N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfuric acid diamide,

5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,

2-thiocyanatomethylthiobenzothiazole,

1,4-dichloro-2,5-dimethoxybenzene,

4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone,

2-thiopyridine 1-oxide,

8-hydroxyquinoline and its copper salt,

2,3-dihydro-carboxanilido-6-methyl-1,4-oxathiyne,

2,3-dihydro-carboxanilido-6-methyl-1,4-oxathiyne 4,4-dioxide,

2-methylfuran-3-carboxanilide,

3 2,5-dimethylfuran-3-carboxanilide,

2,4,5-trimethylfuran-3-carboxanilide,

2,5-dimethyl-N-cyclohexylfuran-3-carboxamide,

N-cyclohexyl-N-methoxy-2,5-diethylfuran-3-carboxamide,

2-methylbenzanilide,

2-iodobenzanilide,

N-formyl-N-morpholine-2,2,2-trichloroethylacetal,

piperazine-1,4-diylbis-(1-(2,2,2-trichloroethyl)-formamide),

1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane,

2,6-dimethyl-N-tridecylmorpholine and its salts,

2,6-dimethyl-N-cyclododecylmorpholine and its salts,

N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine,

N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-piperidine,

1-[2-(2,4-dichlorophenyl)-4-ethyl-1-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole,

1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole,

N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazolyl-urea,

1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-butan-2-one,

1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-butan-2-ol,

1-(4-phenylphenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol,

α-(2-chlorophenyl)-α-(4-chlorophenyl)-5-pyrimidinemethanol,

5-butyl-(2-dimethylamino-4-hydroxy-6-methylpyrimidine,

bis-(p-chlorophenyl)-3-pyridinemethanol,

1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene,

1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene,

and various fungicides, such as

dodecylguanidine acetate,

3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]-glutaramide,

hexachlorobenzene,

DL-methyl-N-(2,6-dimethylphenyl)-N-fur-2-yl alenate,

methyl DL-N-(2,6-dimethylphenyl)-N-(2'-methoxyacetyl)-alanate,

N-(2,6-dimethylphenyl)-N-chloroacetyl-DL-2-aminobutyrolactone,

methyl DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)-alanate,

5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine,

3-[3,5-dichlorophenyl]-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione,

3-[3,5-dichlorophenyl]-1-isopropylcarbamylhydantoin,

N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide,

2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]-acetamide,

1-[2-(2,4-dichlorophenyl)-pentyl]-1H-1,2,4-triazole,

2,3-difluoro-α-(1H-1,2,4-triazol-1-ylmethyl)-benzhydryl alcohol,

N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine,and

1-((bis-(4-fluorophenyl)-methylsilyl)-methyl)-1H-1,2,4-triazole.

Use example

For comparison purposes,cis-2-(imidazol-1-yl-methyl)-2-(4-fluorophenyl)-3-(2,6-difluorophenyl)-oxirane(A) disclosed in DE 3,218,130 was used.

Use example Action on Plasmopara viticola

Leaves of potted vines of the Muller-Thurgau variety were sprayed withaqueous suspensions containing (dry basis) 80% of active ingredient and20% of emulsifier. To assess the duration of action, the plants were setup, after the sprayed-on layer had dried, for 8 days in the greenhouse.Then the leaves were infected with a zoospore suspension of Plasmoparaviticola. The plants were first placed for 48 hours in a watervapor-saturated chamber at 24° C. and then in a greenhouse for 5 days atfrom 20° to 30° C. To accelerate and intensify the sporangiophoredischarge, the plants were then again placed in the moist chamber for 16hours. The extent of fungus attack was then assessed on the undersidesof the leaves.

The results show that active ingredients 113 and 115, applied as 0.05 wt% spray liquors, had a better fungicidal action (95%) than prior artcomparative agent A (60%).

We claim:
 1. Substituted imidazolylmethyloxiranes and substitutedimidazolylpropenes of the general formula I ##STR18## where R¹ and R²are identical or different and each is C₁ -C₈ -alkyl, C₃ -C₈-cycloalkyl, C₅ -C₈ -cycloalkenyl, tetrahydropyranyl, norbornyl,pyridyl, naphthyl, biphenyl or phenyl, each of which is unsubstituted ormono- to trisubstituted by halogen, nitro, phenoxy, amino, alkyl, alkoxyor haloalkyl, each of 1 to 4 carbon atoms,D is oxygen or a single bond,E is H, F, Cl or Br, X, Y and Z are identical or different and each ishydrogen or C₁ -C₃ -alkyl, X, Y and Z not simultaneously being hydrogen,and acid addition salts and metal complexes thereof tolerated by plants.2. Substituted imidazolylmethyloxiranes and substitutedimidazolylpropenes of the general formula I, where R¹ and R² are phenylwhich is unsubstituted or mono- or disubstituted by fluorine, chlorine,bromine or trifluoromethyl.
 3. A fungicidal composition comprising acarrier and a fungicidally effective amount of animidazolylmethyloxirane or an imidazolylpropene of the formula I##STR19## where R¹ and R² are identical or different and each is C₁ -C₈-alkyl, C₃ -C₈ -cycloalkyl, C₅ -C₈ -cycloalkenyl, tetrahydropyranyl,norbornyl, pyridyl, naphthyl, biphenyl or phenyl, each of which isunsubstituted or mono- to trisubstituted by halogen, nitro, phenoxy,amino, alkyl, alkoxy or haloalkyl, each of 1 to 4 carbon atoms,D isoxygen or a single bond, E is H, F, Cl or Br, X, Y and Z are identicalor different and each is hydrogen or C₁ -C₃ -alkyl, X, Y and Z notsimultaneously being hydrogen, and acid addition salt or metal complexthereof tolerated by plants.
 4. A process for combating fungi, wherein afungicidally effective amount of a substituted imidazolylmethyloxiraneor of a substituted imidazolylpropene of the formula I ##STR20## whereR¹ and R² are identical or different and each is C₁ -C₈ -alkyl, C₃ -C₈-cycloalkyl, C₅ -C₈ -cycloalkenyl, tetrahydropyranyl, norbornyl,pyridyl, naphthyl, biphenyl or phenyl, each of which is unsubstituted ormono- to trisubstituted by halogen, nitro, phenoxy, amino, alkyl, alkoxyor haloalkyl, each of 1 to 4 carbon atoms,D is oxygen or a single bond,E is H, F, Cl or Br, X, Y and Z are identical or different and each ishydrogen or C₁ -C₃ -alkyl, X, Y and Z not simultaneously being hydrogen,or an acid addition salt or metal complex thereof tolerated by plants,is allowed to act on the fungi or the materials, areas, plants or seedthreatened by fungus attack.